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Tzalis, Dimitrios. "Coordination compounds as synthetic building-blocks /." Diss., Connect to a 24 p. preview or request complete full text in PDF format. Access restricted to UC campuses, 1998. http://wwwlib.umi.com/cr/ucsd/fullcit?p9824658.
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Santos, Maria Graziela Alvarenga dos. "Síntese e caracterização de compostos de coordenação de nitrato de uranilo aminóxidos aromáticos." Universidade de São Paulo, 2005. http://www.teses.usp.br/teses/disponiveis/46/46134/tde-26092016-150831/.
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Este trabalho descreve a síntese e a caracterização de compostos de coordenação formados a partir do sal nitrato de uranilo hexaidratado e os ligantes piridina-N-áxido e suas três formas isoméricas derivadas (2-picolina-N-áxido, 3-picolina-N-óxido e 4-picolina-N-óxido).. Os complexos foram preparados a partir da reação do sal nitrato de uranilo hexaidratado com os aminóxidos aromáticos em meio etanólico, na proporção 1:2. Os compostos foram caracterizados por análise elementar (CHN), espectroscopia de absorção na região do infravermelho, difração de raios x pelo método do pó, termogravimetrialtermogravimetria derivada (TG/DTG), calorimetria exploratória diferencial (DSC), testes de solubilidade e espectroscopia de emissão na região do visível. Os compostos foram isolados na forma sólida, apresentam coloração amarelada e são praticamente insolúveis na maioria dos solventes. Os resultados analíticos sugerem fórmula geral UO2(NO3)2.2L e as curvas TG/DTG e DSC permitiram avaliar o comportamento térmico dos complexos. Os espectros de absorção no infravermelho indicam que os complexos foram isolados na forma anidra e que a coordenação do ligante ocorre através do oxigênio do grupo NO, Os difratogramas de raios x pelo método do pó não indicam a presença de isomorfismo entre os compostos.As curvas TG/DTG permitiram inferir que o composto UO2(NO3)2.2(pyO) é o mais estáveL As curvas DSC evidenciam o processo de fusão no início da decomposição térmica dos complexos. O produto final corresponde a uma mistura de UO3 e U3O8 como produto final.The synthesis and characterization of complexes or uranyl nitrate with pyridine-N-oxide and the three derivatives isomeric forms (2-picolíne- N-oxide, 3-picoline-N-oxide and 4-picoline-N-oxide) as ligands are described. They were prepared by reaction of hydrated uranyl nitrate with ligands in ethanolic solution (mo1ar ratio 1:2). The compounds were characterized by CHN microanalyticalprocedures, infrared spectroscopy, x ray power diffraction, TG/DTG and emission spectroscopy. The analytical results suggest de general fornula UO2(NO3)2.2L and the NO group oxygen. X ray power difracttion pattems do not indicate the presence of isomphism for this series of compounds. The the compounds have luminescence and the thermal decomposition yield a mixture of UO2 and U3O8 as final product.
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Brayshaw, Simon Keith. "Metal complexes bearing pendant alkynes and metal complexes of N-heterocyclic carbenes." University of Western Australia. School of Biomedical and Chemical Sciences, 2004. http://theses.library.uwa.edu.au/adt-WU2005.0017.
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This thesis is comprised of two parts. The first part describes the synthesis of cyclopentadienyltungsten complexes containing a pendant alkyne group (I), and the subsequent photo-induced intramolecular coordination of the alkyne, forming complexes such as II. Compounds containing intramolecularly coordinated alkynes are rare, and this is the first example using cyclopentadiene as the core ligand. The second part describes the synthesis and structural characterisation of a number of novel metal complexes containing N-heterocyclic carbene ligands, some containing particular functionality for taylored applications. New methods were used to form complexes of rhodium, iridium, silver and gold (eg. III, IV). Structural and spectroscopic properties of the complexes were correlated with electronic characteristics of the ancillary ligands. A number of rhodium and iridium complexes (eg. IV) derived from imidazolium-linked cyclophanes were synthesised and structurally characterised. Complexes of N-heterocyclic carbenes with pendant ionic groups were synthesised, and a preliminary examination of their catalytic activity in water was performed. N-Heterocyclic carbenes complexes containing an electron withdrawing nitro group were synthesised and the effect of the nitro group on metal-ligand bonding was examined.
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Stolberg, Tonie Louis. "Synthesis and properties of bidentate coordination compounds of tin." Thesis, University of Oxford, 1991. http://ora.ox.ac.uk/objects/uuid:ff861007-1ff0-470e-8554-86749bc291a1.
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This Thesis describes the synthesis, structural characterization and properties of some tin(II) and tin(IV) compounds containing bidentate ligands. Chapter 1 describes the main spectroscopic techniques used in the identification of tin(II) compounds; infra-red, 119Sn Mössbauer and n.m.r spectroscopy are outlined, and relevant examples given. A comprehensive listing is given of the main spectroscopic and structural properties of known tin(]3) compounds. Chapter 2 describes the general synthetic methods employed for the formation of tin(II)-oxygen heterocyclic compounds. A range of catecholate and related complexes of tin(II) were synthesized and the role of the substituent investigated with regard to their physical properties, especially their solubilities. The use of 4-nitrocatechol leads to a soluble product, {Sn[O-4-NO2-C6H3O][OC4H8]}>sub>n, which enabled it to be studied spectroscopically and its solid state structure to be determined. The nature of the bonding in {Sn[O-4-NO2-C6H3O][OC4H8]}n was investigated using Extended Hiickel molecular orbital calculations. Chapter 3 describes the chemical reactivity of the novel, soluble, tin(II)-oxygen heterocycle {Sn[O-4-NO2-C6H3O][OC4H8]}n. Reaction with iodine gives SnI2 [O-4-NO2-C6H3O][OC4H8]2. Reaction with the Lewis base such as 1,2-diaminopropane gives Sn[NH2CH2CH(Me)H2N][O-4-NO2-C6H3O][OC4H8], whilst benzyltriethylammonium chloride gives {[Et3BzN][SnCl(O-4-NO2-C6H3O)]}n. The solid-state structure of the compound consists of polymeric chains of [SnCl(O-4-NO2-C6H3O)]- and associated [Et3BzN]+ cations. Reaction with BF3.Et2O gives the adduct F3B.Sn[O-4-NO2- C6H3O][OC4H8]. Reaction with W(CO)5thf gives {(OC)3W.Sn[(O-4-NO2- C6H3O)(OC4H8)]}2 in which the tungsten atoms are believed to be bound η6 to the aromatic rings. Reaction with bis(triphenylphosphine)platinum-ethylene or tris(triphenylphosphine)platinum gives {PtH[PPh3]3}{[μ2-O][μ2-OH][Sn(O-4-NO2- C6H3O)]2}, the anion containing tin(II) and tin(IV) centres. Reaction with RhCl[CNC8H9]3 gives {RhCl[CNC8H9]3[μ2-Sn(O-4-NO2-C6H3O)]}2. Reaction with Ph3PAuCl gives the cluster Au4(PPh3)4(μ2-SnCl3)2, which is the first known example of a compound containing a μ2-SnX3 fragment. In comparison with SnCl2, {Sn[O-4-NO2- C6H3O][OC4H8]}n only weakly inserts into the platinum-chlorine bonds of PtCl2(dppe). Two molar equivalents of SnCl2 reacts with PtCl2(dppe) to give Pt(dppe)(SnCl3)2. Addition of a further equivalent of SnCl2 in the presence of tetraethylammonium chloride gives [Et4N][Pt(dppe)(SnCl3)3]. The platinum centre in this ion has a distorted trigonal bipyramidal geometry. Chapter 4 describes the synthesis of a number of tin(II)-sulphur heterocycles. The reaction between Sn[SC6H4S] and TMEDA gives a soluble adduct, Sn[SC6H4S]TMEDA. A number of tin(II)-nitogen heterocycles were also synthesized. Their intense colours and their instability towards air oxidation indicated that they were monomeric in the solid-state. Chapter 5 outlines the basis for non-linear optical properties, especially their SHG effects. A wide range of tris(catecholato)tin(IV) compounds were synthesized and tested for SHG activity. A number were found to have a significant SHG effect, especially [(O-4- NO,sub>2-C6H3O)3Sn][NHEt3]2, which has an SHG effect 1.33 x urea.
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Eichler, Jack Frederick. "Coordination compounds possessing stannylamines synthesis, characterization and application /." Diss., Available online, Georgia Institute of Technology, 2004:, 2004. http://etd.gatech.edu/theses/available/etd-08242004-084134/unrestricted/eichler%5Fjack%5Ff%5F200412A%5Fphd.pdf.
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Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005.William S. Rees, Jr., Committee Chair ; E. Kent Barefield, Committee Member ; Angus P. Wilkinson, Committee Member ; Z. John Zhang, Committee Member ; Dennis W. Hess, Committee Member. Includes bibliographical references.
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Low, Kam-hung, and 魯錦鴻. "Synthesis, structural characterization and applications of homoleptic organosulfur and organoselenium metal polymers." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2009. http://hub.hku.hk/bib/B43703859.
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Darawsheh, Mohanad D. "Spin crossover supramolecular coordination compounds: design, synthesis and properties." Doctoral thesis, Universitat de Barcelona, 2016. http://hdl.handle.net/10803/400859.
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The results obtained in this thesis demonstrate the importance of supramolecular chemistry for the design of potential new SCO clusters. Starting from synthesizing the suitable ligands with suitable functional groups, novel host-guest systems could be obtained where the guest play a major role in tuning the physical properties of the guest.
Two bis-pyrazolylpyridine lignads, H2L4 and H2L6 were designed and prepared to achieve the assembly of transition metal ions in a triple-stranded helicate fashion where the central cavity can encapsulate different counterions depending on the size of this cavity. The N-H groups found in these ligands which usually directed toward the internal cavity help in the encapsulation of hydrogen acceptor anions. 13 iron-based compounds have been crystallized and studied adding significantly to the helical SCO compounds in the literature. The crystal structure for all the compounds were resolved, which allowed for an extensive study of supramolecular interactions and the influence of these interactions on the magnetic properties of the compounds.
The first part of the thesis deals with spin-crossover dinuclear triple-stranded helicates compounds with encapsulated halide ions using H2L4. Six of such helicates with different encapsulated halide or counter ions were synthesized:
Cl⊂[Fe2(H2L4)3]Cl(PF6)2·5.7CH3OH (1)
Br⊂[Fe2(H2L4)3]Br(PF6)2·4CH3OH (2) Cl⊂[Fe2(H2L4)3]Cl(PF6)2·3CH3OH·1H2O (1a) Br⊂[Fe2(H2L4)3]Br(PF6)2·1CH3OH·1H2O (2a) Cl⊂[Fe2(H2L4)3](I3)3·3(Et2O) (3)
Br⊂[Fe2(H2L4)3](I3)3·3(Et2O) (4)
These isostructural compounds consist of triple-stranded helicates that encapsulate halide ion inside their cavity. The main difference is the kind of outer counterions and lattice solvents which affect dramatically the magnetic properties of these compounds as a result of changing the supramolecular interactions. Changing the halide ion from chloride to bromide in 1 and 2, respectively, shift the spin transition by 30 K. The SCO occur here from [HS-LS] to [HS-HS] upon heating.
Compounds 1a and 2a are the water solvate helicates that produced from single-crystal to single-crystal exchange by exposing the crystals to the ambient water. This exchange leads to important changes; the {X⊂ [Fe2(H2L4)3]}3+ helicate are now symmetric and the two Fe centers are crystallographically identical. This change in the solvent affects dramatically the SCO behavior of the helicates. Two-step SCO from [LS-LS] à [HS- LS]à [HS-HS] states was observed in the bulk magnetic studies. Compounds 3 and 4 consists of {X⊂ [Fe2(H2L4)3]}3+ triple-stranded helicates similar to the one seen in
previous helicates where the counter ions are now three triodide (I3-) linear ions
occupying the outer space formed between the helical strands and the solvent is ether. In these complexes the iron centers remain in the HS state through all the temperatures.
The change of the solvents used in the reaction yielded different supramolecular compounds using the same ligands H2L4. Dimerized mononuclear helicates
{X⊂[Fe(H2L4)3]2}3+ was prepared where a halide ion is encapsulated inside the cavity
formed by the intercalating dimers. Five dimerized triple-stranded helicates are presented in this thesis:
Cl⊂[Fe(H2L4)3]2(OH)(PF6)2·H2O (5).
Cl⊂[Fe(H2L4)3]2(FeCl4)3·2C3H6O·4C7H8 (6).
Br⊂[Fe(H2L4)3]2(OH)(PF6)2·H2O (7).
I⊂[Fe(H2L4)3]2(PF6)2.23(I)0.21(I3)0.56·2CH3OH (8)
I⊂[Fe(H2L4)3]2(I)2(I3)0.6(OH)0.4·0.6H2O·2CH3OH·2C3H6O (9)
In every mononuclear helicate, one pyrazolyl-pyridine side of each ligand is not coordinated to any metal ion. The SCO behavior of the dimer is also affected by the nature of the halide ions which make hydrogen bonding with the N-H groups of the pyrazole rings.
Using the ligand H2L6, the encapsulation of [M(III)(ox)3]3- (M = Fe and Cr; ox = oxalate) metal complexes inside the helical cavity of [Fe2(H2L6)3]4+ was achieved. Two of such triple-stranded helicates are presented in this thesis:
Fe(C2O4)3⊂[Fe2(H2L6)3](BF4)·4CH3OH·3.7H2O (10).
Cr(C2O4)3⊂[Fe2(H2L6)3](BF4)·1.4CH3OH·6H2O (11).
The Fe(II) ions of the helicate exhibit SCO behavior and LIESST effect in the case of the encapsulated chromium oxalate complex. Interestingly, the guest [Cr(III)(ox)3]3- exhibits SIM-like behavior at low temperatures. This is the first example where a host- guest system exhibits both LIESST effect and SIM behavior.Dos ligandos bis-pyrazolylpyridine, H2L4 y H2L6 fueron diseñados y preparados para sintetizar ensamblajes con iones de metales de transición en forma de helicatos de cadena triple donde la cavidad central puede encapsular diferentes contraiones en función del tamaño de esta cavidad. 13 compuestos a base de hierro se han cristalizado y estudiado, con la adición de manera significativa de compuestos helicoidales con SCO de la literatura. La estructura cristalina de todos los compuestos fueron resueltas, lo que permitió un amplio estudio de las interacciones supramoleculares y la influencia de estas interacciones sobre las propiedades magnéticas de los compuestos. La primera parte de la tesis trata de compuestos helicoidales dinucleares de cadena triple presentando transición de espín con iones haluro encapsulados utilizando H2L4. Estos compuestos isoestructurales consisten en helicatos de cadena triple que encapsulan iones haluro dentro de su cavidad. La principal diferencia es el tipo de contraiones exteriores y disolventes de cristalización que afectan dramáticamente las propiedades magnéticas de estos compuestos, como resultado de cambiar las interacciones supramoleculares. El cambio del ión haluro, de cloruro a bromuro, da un cambio de la transición de espín de unos 30 K. En los complejos metanólicos, la SCO se producen por calentamiento, a partir de [HS-LS] a [HS-HS], donde los estados de espín mixtos se consigue gracias a diferente distorsión alrededor de los iones metálicos, como resultado de diferentes enlaces de hidrógeno supramolecular cerca de los dos. Los helicatos con agua se producen a partir de una transformación cristal-cristal, mediante la exposición de los cristales a agua a temperatura ambiente. Este cambio en el disolvente afecta dramáticamente el comportamiento del SCO. Dos pasos en el SCO ([LS-LS] à [HS-LS] à [HS-HS]) se observarón en los estudios magnéticos. El cambio de los aniones a triyoduro (I3-) estabilizan el estado HS en todas las temperaturas medidas. El cambio en los disolventes utilizados en la reacción produjo diferentes compuestos supramoleculares utilizando el mismo ligando H2L4. Diferente helicatos mononucleares dimerizados {X⊂[Fe(H2L4)3]2}3+ fueron preparado donde se encapsula un ion haluro dentro de la cavidad formada por los dímeros intercalantes. En cada helicato mononuclear, un lado pirazolilo-piridina de cada ligando no se coordina a ningun ion metálico. El comportamiento de SCO del dímero también se ve afectada por la naturaleza de los iones haluro que forman con los enlaces de hidrógeno con los grupos N-H de los anillos de pirazol. Utilizando el ligando H2L6, se logró la encapsulación de complejos metálios de tipo [M(III)(ox)3]3- (M = Fe y Cr; ox = oxalato) dentro de la cavidad helicoidal [Fe2(H2L6)3]4+. Los iones Fe (II) del helicato exhiben SCO y efecto LIESST en el caso del complejo de cromo oxalato encapsulado. Curiosamente, el invitado [Cr(III)(ox)3]3- presenta un comportamiento de SIM a bajas temperaturas. Este es el primer ejemplo en el que un sistema hospedador-huésped exhibe tanto efecto LIESST y comportamiento SIM.
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Leung, Hiu-chi, and 梁曉詞. "Syntheses, reactivities and biological activities of ruthenium azido, nitrido and nitrosyl complexes supported by tetradentate tertiaryamine ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B43703732.
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Kleinhans, Dewald Johannes. "Studies in the synthesis of benzoxazole compounds." Thesis, Stellenbosch : Stellenbosch University, 2015. http://hdl.handle.net/10019.1/97900.
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Thesis (PhD)--Stellenbosch University, 2015.ENGLISH ABSTRACT: Benzoxazoles are an important class of π-electron-excessive, benzene-fused heterocyclic compounds found in natural products and display a wide range of pharmacological applications. It is therefore a widely used starting scaffold for drug and agrochemical discovery programs. Other applications include: chiral auxiliaries in asymmetric reactions, chiral receptors for the resolution of racemic mixtures, fluorescent whitening dyes, various photochromic materials and as ligands for a wide range of catalytic reactions. Due to our interests in resorcinarenes, we came across 4-hydroxybenzoxazoles, a structural motif that has not been explored as potential asymmetric ligands. In this thesis it was attempted to investigate the synthesis, functionalisation and coordination chemistry of these compound class and finally look at a method of synthesising chiral 4-hydroxybenzoxazoles from amino acids. A small library of achiral 4-hydroxybenzoxazoles were synthesised in good yields. These compounds were then reacted with various transition metals, of which only the Pd-salts proved to return any usable compounds. The first structural evidence of the bonding of 4- hydroxybenzoxazoles was recorded from single crystal X-ray diffraction analysis of the coordination compounds that formed. Different coordination modes were recorded, depending on the ligand and the Pd-salt used. The PdCl2 compounds were also tested for catalytic activity with a Heck reaction, showing good conversions for the reaction between iodobenzene and styrene to form stilbene. Further examination pointed to the ligands playing an insignificant role in the reaction and the products possibly due to only the PdCl2’s reactivity. During this period it was also attempted to functionalise the phenol group with P(III) groups and repeat the coordination and catalytic studies. Efforts to synthesise these compounds were not successful, with oxidation of the P(III) to P(V) groups or degradation of these compounds. Efforts to synthesise these via phosphorous protection, utilising BH3 or the in situ trapping of the compounds with transition metals, were also not successful. During the trapping experiments the phosphinite and Pd-salt formed a re-arranged product that is a known and useful catalyst on its own. Finally a small library of chiral benzoxazoles and 4-hydroxybenzoxazoles were synthesised, starting from amino acids and utilising a Mitsunobu reaction to perform the ring closing. Antimicrobial tests with these compounds did not return any appreciable results.
AFRIKAANSE OPSOMMING: Bensoksasool is 'n belangrike klas van π-elektron-ryk, benseen-saamgesmelte heterosikliese verbindings wat in natuurlike produkte voorkom en 'n wye verskeidenheid van farmakologiese funksies vertoon. Dit is dus 'n baie algemene basis struktuur vir dwelm- en landbouchemiese ontdekkings programme. Ander gebruike sluit in: chirale ligande in asimmetriese reaksies, chirale reseptore vir die resolusie van rasemiese mengsels, fluoresserende verwittings kleurstowwe, verskeie fotochromiese materiaal en as ligande vir 'n wye verskeidenheid van katalitiese reaksies. As gevolg van ons belangstelling in resorsinarene, het ons op 'n strukturele motief afgekom wat nog nie ondersoek is as potensiële asimmetriese ligande nie, die 4- hidroksiebensoksasole. In hierdie tesis is gepoog om die sintese, funksionalisering en koördinasie chemie van hierdie klas verbindings te ondersoek en uiteindelik 'n metode te ontwikkel om die sintese van chirale 4-hidroksiebensoksasole vanaf aminosure te bewerkstellig. 'n Klein biblioteek van achirale 4-hidroksiebensoksasole was gesintetiseer in goeie opbrengste. Hierdie verbindings was toe behandel met verskeie oorgangsmetale, waarvan slegs die Pdsoute enige bruikbare verbindings gevorm het. Die eerste strukturele bewyse van die binding van die 4-hidroksiebensoksasole is aangeteken met behulp van enkelkristal X-straaldiffraksie ontleding van die koördinasieverbindings wat gevorm is. Verskillende koördinasie mode is aangeteken, afhangende van die ligand en die Pd-sout wat gebruik was. Die PdCl2 verbindings is ook vir katalitiese aktiwiteit met 'n Heck reaksie getoets. Die reaksie het baie goeie omskakeling gewys vir die reaksie tussen iodobenseen en stireen na stilbeen. Verdere ondersoeke het getoon dat die ligande nie ‘n beduidende rol in die reaksie speel nie en die produkte moontlik slegs as gevolg van die PdCl2 se reaktiwiteit is. Gedurende hierdie tydperk was daar ook probeer om die fenol groep met P(III) groepe te funksionaliseer. Met die uitgangstowwe sou die koördinering en katalitiese studies herhaal word. Pogings om hierdie verbindings te sintetiseer was nie suksesvol nie, met oksidasie van die P(III) na P(V) groepe of afbreking van hierdie verbindings. Pogings om dit te sintetiseer via fosfor beskermingstegnieke, deur gebruik te maak van BH3 of die in situ vasvang van die verbindings met oorgangsmetale, was ook nie suksesvol nie. Gedurende die vasvang eksperimente het die fosfien en PdCl2 ‘n herrangskikkings-produk gevorm wat op sy eie ‘n bekende en nuttige katalisator is. Ten slotte was 'n klein biblioteek van chirale bensoksasole en 4-hidroksiebensoksasole gesintetiseer, vanaf aminosure. Om die ringsluiting te bewerkstellig was ‘n Mitsunobu reaksie gebruik. Antimikrobiese toetse met hierdie verbindings het nie enige noemenswaardige resultate opgelewer nie.
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Lees, Anthony M. J. "Synthesis and characterisation of coordination compounds of lanthanides with diphosphonates." Thesis, Staffordshire University, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.325973.
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Oosthuizen, Lukas Marthinus. "New platinum coordination compounds : their synthesis, characterization and anticancer application." Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/d1018795.
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The aim of this thesis was to investigate the properties of novel platinum compounds with possible potential as anticancer agents, and to determine how their behaviour could lead to a better understanding of the chemistry involved. The final criteria were improvement of their anticancer behaviour. Since many questions are still unanswered as to the role of sulfur in anticancer action, studies were undertaken to synthesize novel platinum(II) complexes having non-leaving groups consisting of a combination of an aromatic nitrogen and thioetherial sulfur capable of forming a five membered ring upon coordination. The structural unit was 1-methyl-2-methylthioalkyl/aryl. Numerous complexes formed by these ligands each having chloro, bromo, iodo and oxalato leaving groups were then fully characterized. The results obtained by the various synthetic methods were compared and explained in terms of the chemistry involved. The role of the sulfur donor was indicated in both the halo- and oxalato-complexes and proved to be strongly influenced by the nature of the leaving groups. Their differences are reflected in their anticancer behaviour. The study was extended to mononitroplatinum(IV) complexes, in view of the kinetically stable platinum(IV) compounds and advantages related to this. A specific mononitroplatinum(IV) complex which proved to have good anticancer and STAT 3 properties could according to the literature not be synthesized successfully in a good yield and a high degree of purity. The results of extensive studies showed that the main problem centred around the simultaneous reactions in equilibrium during the synthesis. A number of these species formed as a result of side reactions could be identified and their close separation factors indicated chromatographically. The mechanism of these reactions and the unstable intermediate species involved could be rationalized and compared to analogues in the literature. All the complexes studied were characterized by spectral and thermal methods both in solution as well as the solid state. Their anticancer behaviour towards three anticancer cell lines (Hela, MCF 7, Ht 29) were determined and acted as a guide towards possible structural modifications for their improved capability. Three crystal structures of platinum(II) complexes were determined. The extent of the ionization of the platinum(II) complexes as well the redox potentials (Pt(II) / Pt(IV)) of the platinum(IV) complexes were particularly important factors pertaining to their anticancer action.
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Gorlamari, Kranthikkumarreddy. "Synthesis and self-assembly of coordination lipid polymers." To access this resource online via ProQuest Dissertations and Theses @ UTEP, 2008. http://0-proquest.umi.com.lib.utep.edu/login?COPT=REJTPTU0YmImSU5UPTAmVkVSPTI=&clientId=2515.
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Low, Kam-hung. "Synthesis, structural characterization and applications of homoleptic organosulfur and organoselenium metal polymers." Click to view the E-thesis via HKUTO, 2009. http://sunzi.lib.hku.hk/hkuto/record/B43703859.
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Kleyi, Phumelele Eldridge. "Solvent-free synthesis of bisferrocenylimines and their coordination to rhodium (I)." Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/1053.
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Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
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Lentz, Nicolas. "Metallylene-sulfur compounds : synthesis, characterization and applications in coordination and catalysis." Thesis, Toulouse 3, 2018. http://www.theses.fr/2018TOU30274/document.
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Ce travail présente la synthèse de ligands mixtes germylène-sulfoxyde qui ont été utilisés en chimie de coordination avec plusieurs métaux de transitions et finalement appliqués en catalyse de transfert d'hydrogène. Une seconde partie de ce travail est axée sur la synthèse de nouveaux métallylènes stabilisés par un sulfonimidamide qui ont été appliqués en catalyse de polymérisation. Le premier chapitre présente l'état de l'art des germylènes avec leurs synthèses, modes de stabilisations et finalement leur chimie de coordination et leurs applications en catalyse. Les sulfoxydes seront aussi décrits pour leur application en tant que ligands hémilabiles. Le second chapitre décrit la synthèse de ligands germylène-α-sulfoxide avec une diversité structurale (cyclohexyle, tBu, tolyle..) et avec différents degrés d'oxydation du souffre (thioéther, sulfoxyde et sulfone). La chimie de coordination a permis la synthèse de complexes bis-germylène du groupe IV, bidentes du ruthénium ainsi que monodentes du ruthénium. Le troisième chapitre présente l'extension de la méthodologie à la formation de ligands germylène-β-sulfoxide. L'influence du groupement espaçant les deux entités sur la chimie de coordination a été étudiée et montre la formation de complexes bidentates du groupe IV. La coordination du ruthénium a mené à la surprenante synthèse d'un complexe bis-ruthénium caractérisé par diffraction des rayons X. Finalement, la nouvelle architecture a permis d'obtenir des complexes de nickel (0) dont une structure avec des ligands carbonyles permettant une comparaison TEP. Le chapitre quatre présente la synthèse de nouveaux ligands, analogues des amidinates, pour la stabilisation des métallylènes avec un atome central soufré. L'effet apporté sur les métallylènes par ces nouveaux ligands sulfonimidamides a été étudié par calcul DFT. Le dernier chapitre est centré sur l'application de plusieurs complexes de ruthénium en catalyse de transfert d'hydrogène avec plusieurs substrats carbonylés. L'utilisation de stannylènes stabilisés par des ligands sulfonimidamides a été étudiée en catalyse de polymérisation de la ε-caprolactoneThis work concerns the synthesis of mixed germylene-sulfoxide ligands that were involved in coordination chemistry with several transition metals and finally applied in hydrogen transfer catalysis. In a second part, the synthesis of new metallylenes stabilized by a sulfonimidamide group was develop, which were applied in polymerization catalysis. The first chapter is centered on the state of the art of germylenes with their synthesis, their stabilization and finally their coordination chemistry and applications in catalysis. Sulfoxides will also be described for their potential as hemilabile ligands. The second chapter describes the synthesis of germylene-α-sulfoxide ligands as structurally tunable structures (cyclohexyl, tBu, tolyl..) and with different oxidation states of the sulfur atom (thioether, sulfoxide and sulfone). The coordination chemistry led to the formation of bis-germylene group IV complexes, bidentate-ruthenium and monodentate ruthenium complexes. The third chapter shows the extension of the methodology to the formation of germylene-β-sulfoxide ligands. The influence of the spacer between the two entities on the coordination chemistry was studied and shows the formation of bidentate group IV complexes. Coordination to ruthenium led to obtain a surprising bis-ruthenium complex characterized by X-ray diffraction analysis. Finally, the novel architecture allowed to obtain two nickel (0) complexes, one of them including carbonyl ligands permitting a TEP comparison. The fourth chapter is centered on the synthesis of new ligands, analogue of amidinate substituents for metallylene stabilization with a central sulfur atom. The effect brought to the metallylene center by the sulfonimidamide was studied by DFT calculations. The last chapter concerns the application of several ruthenium complexes in hydrogen transfer reaction with various carbonyl compounds. The use of sulfonimidamide stannylenes was also investigated in polymerization catalysis of ε-caprolactone
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Lin, Zhuojia. "Hydrothermal synthesis of metal coordination polymers using mixed pyridine-carboxylate ligands /." View abstract or full-text, 2005. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202005%20LIN.
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Tse, Hiu Wah. "Hydrothermal synthesis of metal carboxylate polymers using high coordination number metals /." View abstract or full-text, 2004. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202004%20TSE.
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Lesikar, Leslie Anne. "The synthesis and structural characterization of main group and transition metal complexes supported by nitrogen based ligands." [Fort Worth, Tex.] : Texas Christian University, 2008. http://etd.tcu.edu/etdfiles/available/etd-01162009-164206/unrestricted/Lesikar.pdf.
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Salinas, Uber Jorge. "Design and synthesis of photoswitchable coordination complexes." Doctoral thesis, Universitat de Barcelona, 2016. http://hdl.handle.net/10803/399911.
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One of the main objectives of this thesis was the synthesis of new chelating ligands containing a photochromic unit able to change its conformation upon light irradiation. This isomerization should serve to modify the magnetic behavior of the new coordination compounds, formed upon reaction of transition metals or lanthanides, assembled within the phtochromic ligands. Whith these aims, the synthesis of 5 new ligands has been achieved, which have been characterized successfully. Subsequently, the preparation of 22 coordination compounds with these ligands has been accomplished. The crystallographic study of these coordination compounds has been very important for the complete understanding of the magnetic and photohromic properties. Regarding the crystal structures, in Chapter 1, the distinct photochromic properties of the complexes discussed was rationalized in light of the structural information. The results show that crystal design may constitute an interesting way for modulating the properties of the solid state photoactivity. Two new ligands were synthesized in Chapter 3, based on beta diketone moieties, which additionally, are functionalized with a phenol group. Those groups together form an excellent chelating pocket to introduce metal arrays. Importantly, those arrays can be formed as pair of heterometallic dimers, whose ground state exhibit in some cases S=1/2 systems, thus providing a pair of spins ½ well defined within the molecule. This feature can be exploited in the context of quantum computing by studying the quantum coherence of these spin. Indeed, coherence times of thousands of nanosecond can be measured at low temperature.. Two other new ligands, have been presented in Chapter 4. These have been synthesized via Schiff base condensation. Similar two the beta diketones, these ligands are able to perform fast and excellent photochromism, in addition to the cis/trans isomerizations that can undergo themselves. While those isomerizations have not been studied, they could be used as gate-reactivity, adding more versatility to these compounds. The chelating pockets of these ligands are very useful regarding to the coordination ability with lanthanides and transition metals. Single molecule magnet behavior has been observed in a dysprosium cluster. Finally, in Chaper 5, the synthesis of a new photochromic ligand containing a pyridine-pyrazole moiety, has been tested for the preparation of a Fe(II) spin crossover helical system. This has shown to be a good candiadate as part of new hybrid devices, because the excellent resistance to the fatigue, the different fluorescent behavior and the SCO features.Durante el transcurso de esta tesis, se han sintetizad nuevos ligandos quelantes que contienen una unidad fotocrómica, capaz de cambiar su conformación tras la irradiación de luz. Esta isomerización debe servir para modificar la interacción magnética de los nuevos compuestos de coordinación, basados en los mencionados nuevos ligandos. Se ha logrado la síntesis de 5 nuevos ligandos y la preparación de 22 compuestos de coordinación. El estudio cristalográfico de estos compuestos de coordinación ha sido muy importante para la comprensión completa de las propiedades magnéticas y fotocrómicas. En el Capítulo 2, las propiedades fotocrómicas de distintos complejos fueron racionalizadas a la luz de la información estructural. Los resultados muestran que el diseño previo puede constituir una buena herramienta para la modulación de las propiedades del estado sólido. Dos nuevos ligandos se sintetizaron en el Capítulo 3, basado en dicetonas. Estas matrices pueden formar pares de dímeros heterometálicos, cuyos estados fundamentales, S = ½, sistemas, pueden ser explotados en el contexto de la computación cuántica mediante el estudio de la coherencia cuántica del espín. En el Capítulo 4, otros dos nuevos ligandos fotocrómicos y sus complejos de coordinación con los lantánidos y metales de transición han sido caracterizados con tal de ver su utilidad en el campo de imanes unimoleculares. Finalmente, en el Capítulo 5, la síntesis de un nuevo ligando fotocrómico que contiene un grupo piridina-pirazol, se ha probado para la preparación de un sistema helicoidal de Fe (II) con transición de espín. Este ha demostrado ser un buen candidato como parte de nuevos dispositivos híbridos, debido a la excelente resistencia a la fatiga, el diferente comportamiento fluorescente y su capacidad para producir una transición de espín.
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Choi, Ming Fai. "Design and synthesis of coordination polymer gels and high dichroic ratio azo dyes /." View Abstract or Full-Text, 2002. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202002%20CHOI.
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Ghebregziabiher, Berhe Haile. "Synthesis of chiral thiourea ligands and their transition metal complexes." Thesis, Stellenbosch : Stellenbosch University, 2003. http://hdl.handle.net/10019.1/53610.
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Thesis (MSc)--Stellenbosch University, 2003.ENGLISH ABSTRACT: Modification of chitosan with benzoylisothiocyanate was attempted, however due to solvent problem the study was left incomplete till appropriate solvent is designed. N,N-diethyl-N -camphanoylthiourea (HL8), N-piperidyl-N '-camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthiourea (HL10) and N,N-diethyl-N -adamantylcarbonyl thiourea (HL11)have been synthesised and characterised for the first time. Two of these ligands HL8 and HL11, were used to form a number of transition metal complexes, namely H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], translcis-[Zn(L 8_S,0)2], translcis-[Pt(L 8_S,0)2], Ag2[(HL8-S)(L-J.1-S,O)]2, translcis- [Ni(L11-S,O)2]and translcis-[Cu(L11_S,O)2]. The new products are fully characterised by means of MS, IR spectroscopy, NMR spectroscopy, elemental (C, H, Nand S) analysis and melting point determinations. The H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8- S,O)2], trans-[Cu(L8-S,O)2] and Ag2[(HL8-S)(L-J.1-S,O)]2 are also characterised by Xray diffraction analysis. The structure of the new chiral N,N-dialkyl-N' -camphanoylthiourea ligand (HL8) has a significant effect on its coordination chemistry with transition metal ions. This ligand forms H30+ {fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,O)2] and Ag2[(HL8- S)(L8-J.1-S,O)]2 complexes with the Co(II), Ni(II), Cu(II) and Ag(I) metal ions respectively. The spectroscopic and X-ray diffraction results of these complexes indicate a bidentate mode of coordination of the ligand (with its Sand °donor atoms) to the Co(II), Ni(II) and Cu(II) metal ions. The reaction of this ligand with silver(I) however affords the formation of a binuclear silver(I) complex exhibiting monodentate and bidentate modes of coordination within the same complex. The exclusive formation of trans-[Cu(L8-S,0)2] is a new phenomenon for the HL type thiourea ligands with Sand °donor atoms. Up to this point a maximum of 15 % trans-isomer has been reported in ltterature." All the transition metal complexes made with HL8and HL11are air stable in both the liquid and solid states except the H30+{fae-[Co(L 8-S,Ob]} Interestingly the deep green fae- H30+{fae-[Co(L8-S,Obn complex is air sensitive and the Co(II) oxidizes to Co(III) in the complex by atmospheric O2. The oxidation of Co(II) to Co(III) in the complex is confirmed by 1Hand 13CNMR spectra as well as by UV-Visible spectra of the complex. The NMR spectra of the complexes indicated the presence of one isomer in each complex except for the NMR spectra of the platinum complex of the HL8 ligand. The presence of the minor trans-[Pt(L8-S,Q)21 isomer in combination with the major cis-[Pt(L8-S,Q)21 isomer in the platinum complex was indicated by the 1H, 13Cand 195ptNMR spectra of the complex.
AFRIKAANSE OPSOMMING: Pogings om chitosan met benzoylisothiocyanate te modifiseer is onvoltooid gelaat weens die gebrek aan'n geskikte oplosmiddel. N,N-diethyl-N -carnphanoylthiourea (HL8), N-piperidyl-N -camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthlourea (HL10) en N,N-diethyl-N -adamantylcarbonyl thiourea (HL11) is vir die eerste keer gesintetiseer en gekarakteriseer. Twee van die ligande, HL8 en HL11, is gebruik om verskeie oorgangsmetaalkomplekse te berei, nl. H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], trans/cis-[Zn(L8 - S,0)2], trans/cis-[Pt(L8-S,0)2], Ag2[(HLB-S)(L-jl-S,0)]2, trans/cis-[Ni(L11-S,0)2] en trans/cis-[Cu(L11_S,0)2]. Die nuwe produkte is volledig gekarakteriseer deur middel van MS, IR spektroskopie, KMR spektrometrie, elemente (C, H, N en S) analise en smeltpuntbepaling. Die komplekse H30+{fao-[Co(L8-S,0)3n, cis-[Ni(L8-S,0)2], trans- [Cu(L8-S,0)2] en Ag2[(HLB-S)(L-jl-S,0)]2 is ook deur middel van X-straaldiffraksieanalise gekarakteriseer. Die struktuur van die nuwe chirale N,N-dialkyl-N'-camphanoylthiourea ligand (HL8) het In beduidende invloed op die koordinasie van hierdie ligand met oorgangsmetaalione. Die ligand vorm H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,0)2] en Ag2[(HL8-S)(L8-Il-S,0)]2 komplekse met Co(ll)-, Ni(II)-, Cu(II)- en Ag(I)-ione respektiewelik. Spektroskopiese en X-straaldiffraksie-analise van die komplekse toon dat die ligande op 'n bidentate wyse d.m.v. die S- en O-donoratome met Co(II), Ni(lI) en Cu(lI) koordineer. Die reaksie van hierdie ligand met Ag(I)-ione lei egter tot die vorming van 'n dikernige silwer(I)-kompleks waarin die ligande monodentaat (S) en bidentaat (S en 0) aan die metaal gebind is. Die vorming van uitsluitlik die trans-[Cu(L8-S,0)2] in die reaksie van HL8 met Cu(lI) is 'n besondere fenomeen in die chemie van hierdie tipe ligande; in die literatuur word melding gemaak van slegs een ander trans-kompleks met hierdie ligande, en dan wel met 'n maksimum opbrengs van 15%.29 Alle oorgangsmetaalkomplekse met HLB en HL11 is stabiel indien blootgestel aan lug, ongeag of die verbindings opgelos word of in die vastetoestand verkeer, behalwe H30+{fao-[Co(L8-S,Ohn. Die diep-groen gekleurde H30+{fao-[Co(L8-S,Ohn)3]} kompleks is lugsensitief; Co(lI) word deur lugsuurstof na Co(lIl) ge-oksideer. Die oksidasie in die kompleks kan deur middel van 1H en 13CKMR spektrometrie sowel as UV-sigbare spektrofotometrie bevestig word. Die KMR spektra van alle komplekse dui op die teenwoordigheid van slegs een isomeer in oplossing, behalwe in die geval van die platinum(lI) kompleks met HL8. Die teenwoordigheid van lae konsentrasies trans-[Pt(L8-S,0)2] isomeer tesame met veel hoër konsentrasies van die cis-[Pt(L8 -S,O)2] isomeer word deur 1H, 13Cen 195ptKMR spektroskopie aangedui.
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Gietz, Twyla Mae, and University of Lethbridge Faculty of Arts and Science. "Lithium complexes of ketoimines and novel alkynyl imines and diimines : discoveries in the attempted synthesis of PACNAC." Thesis, Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry, c2010, 2010. http://hdl.handle.net/10133/2481.
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Two different methodologies were used to attempt the synthesis of a novel P‐N ligand,
denoted as PACNAC for the similarity to the analogous NACNAC and ACAC ligands.
Although the synthesis of PACNAC was not successful, each methodology led to interesting
discoveries. First, a number of lithium complexes of ketoimines were isolated and studied by Xray
crystallography and NMR spectroscopy revealing some interesting substituent based effects
on the structure, solubility and solution state behaviour. The X‐ray data of the two known and
two related novel ketoimines were also collected and compared to the lithium complexes.
Secondly, the synthesis of novel alkynyl imines along with the new alkynyl diimines by novel
synthetic routes and studied by x‐ray crystallography, NMR, electrochemistry, and UV‐Visible
spectra.xvi, 134 leaves : ill. (some col.) ; 29 cm + 1 CD-ROM
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Richards, Victoria Jane. "Synthesis of fluorescent and redox active compounds for incorporation into metal-organic coordination polymers." Thesis, University of Nottingham, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.602423.
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This thesis details the synthesis of fluorescent and redox active compounds for their incorporation into metal-organic coordination polymers. In particular, we report the synthesis of ligands bearing flexible imidazolate and/or carboxylate donors, their reaction with first row transition metal ions and the structural properties of the resulting materials. Chapter 1 introduces the properties, synthesis and applications of metal-organic coordination polymers, in particular crystalline three -dimensional (3~) frameworks, with reference to notable successes within the field. Chapter 2 details the synthesis of five metal-organic coordination polymers based on a novel 2,5-bis(3-(1-imidazolyl)propylcarbamoyl)terephthalate ligand and Zn2+, C02+, Mn2+ and Cu 2+ cations. The coordination environments and structural connectivities within each are compared, with particular attention paid to a rare example of Mn2+ -based supramolecular tological isomers. In Chapter 3 we investigate the use of a N,N'-bis(3-(1 -imidazolyl)propyl)-l,4,5,8- naphthalene-tetracarboxylicdiimide ligand for the formation of nano-scale metalorganic coordination polymers (NCPs). In particular, we examine the effect of both nature of metal ion and starting material concentration on particle size and morphology. Synthesis of comparable crystalline macro-scale materials and subsequent spectroscopic studies allow us to draw conclusions on the effect of metal ion on polymer dimensionality and NCP morphology: whilst two-dimensional (20) Mn(II) -based coordination sheets adopt a nano-rod morphology, onedimensional (10) Cu(II)-based chains form nano-spheres. Chapter 4 details the synthesis of porphyrin ligands bearing flexible imidazolate or carboxylate donors. We report both 10 and 20 coordination polymers based on a 5,15-dimesityl- 10,20-bis(4-phenylacetate)porphyrin ligand and Mn2+ ions, and iii both networks are unusual in that they comprise free base porphyrins and hydrogen bond with encapsulated uncoordinated ligand to afford 2D and 3D frameworks respectively. In Chapter 5 we report a series of borondipyrrin (BODIPY) compounds and investigate the effect of functional and positional substitutions on the electrochemical and optical properties of these chromophores. We further characterise the optical properties of electrochemically generated BODIPY anions and cations and examine the locations of the unpaired electrons of these species via density functional theory calculations and electron paramagnetic resonance spectroscopy. The series of compounds extends into the first examples of BODIPY dimers connected via their boron centres and we detail efforts to incorporate these species into metal-organic coordination polymers. iv
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Price, David James 1976. "Synthesis, structure and magnetism in clusters and networks containing dicyanamide and related ligands." Monash University, School of Chemistry, 2003. http://arrow.monash.edu.au/hdl/1959.1/9365.
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James, Lara. "An investigation into 'green' energetic materials, by the synthesis of novel main group coordination compounds." Thesis, University of Sheffield, 2014. http://etheses.whiterose.ac.uk/5335/.
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Schauer, Philip A. "Organometallic synthons for highly conjugated redox-active materials." University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2009. http://theses.library.uwa.edu.au/adt-WU2009.0166.
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[Truncated abstract] This thesis describes various synthetic approaches toward the synthesis of highly conjugated complexes incorporating multiple transition metal centres. Particular attention is given to the synthesis of mononuclear complexes that allow for the facile assembly of discrete oligo- and poly-nuclear complexes in a controlled, stepwise fashion. Conjugated multi-metallic materials are of interest on account of their unique photophysical and electronic properties, with a particular emphasis on elucidating the nature of intramolecular communication between multiple metal centres. Chapter 1 provides a survey of these topics and current research efforts in the field. Chapter 2 describes the synthesis of Group-VIII allenylidene complexes incorporating a terminal bipyridyl moiety that provides a site for further coordination. The new compound 9-hydroxy-9-ethynyl-4,5-diazafluorene was synthesised, and reaction of this proligand with a coordinatively unsaturated metal fragment yields the allenylidene complexes [MCl(PnP)2=C=C=(4,5-diazafluoren-9-yl)]PF6 (M = Ru, PnP = dppm, dppe, dmpe; M = Os, PnP = dppm) and [CpRu(dppe)=C=C=(4,5-diazafluoren- 9-yl)]PF6. The dmpe-ligated complex is particularly susceptible to decomposition, though it was possible to obtain partial spectroscopic characterisation in addition to a single-crystal X-ray structural determination. The remaining allenylidene complexes are stable compounds readily characterised by standard spectroscopic and electrochemical means, with the bis(diphosphine) complexes characterised by single crystal X-ray structural determinations. ... Reactions of the proligand with [RuCl(PnP)2]+ (PnP = dppm, dppe) led to the isolation of a product spectroscopically consistent with the formation of the target cationic allenylidene complexes, though the complexes were not readily purified and the identity of the accompanying anion was not elucidated. The new compound 4-hydroxy-4- ethynyl-cyclopentadithiophene was also prepared, though the compound was found to be highly unstable and susceptible to rapid decomposition. The derived allenylidene complexes [RuCl(PnP)2=C=C=(4-cyclopentadithiophene)]PF6 (PnP = dppm, dppe) were isolated in a pure form and the complexes stable toward spontaneous decomposition. The thienyl-derived allenylidene complexes were characterised by spectroscopic and electrochemical techniques, with a single-crystal X-ray structural determination undertaken for [RuCl(dppm)2=C=C=(4-cyclopentaditiophene)]PF6. Electrochemical properties are significantly different between the complexes, and also show significant variation between electrodes and solvents. The terminal thienyl substituents are electroactive and show one or two oxidation processes consistent with oligomerisation of the thienyl moiety in dichloromethane solvent, and in acetonitrile solvent cyclic voltammograms are consistent with the deposition of an electroactive film on the electrode surface. The electro-polymerisation of the thienylallenylidene complexes offers a promising new route toward multi-metallic allenylidene complexes.
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Wang, Junfeng [Verfasser], and Martin [Akademischer Betreuer] Dressel. "Synthesis, magnetism and organisation of molecular coordination compounds for molecular spintronics / Junfeng Wang ; Betreuer: Martin Dressel." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2016. http://d-nb.info/1118370252/34.
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Amawi, Rema Mouawya Klausmeyer Kevin Kenneth. "Synthesis and characterization of silver(I) salts with amino methyl pyridines containing phosphines novel complex formation upon ratio, anion, or ligand changes /." Waco, Tex. : Baylor University, 2008. http://hdl.handle.net/2104/5180.
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Leitl, Julia [Verfasser], and Robert [Akademischer Betreuer] Wolf. "Synthesis of Novel Phosphinine Coordination Compounds and their Reactivity toward small Molecules / Julia Leitl ; Betreuer: Robert Wolf." Regensburg : Universitätsbibliothek Regensburg, 2020. http://d-nb.info/1220080454/34.
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Straistari, Tatiana. "Synthesis and study of coordination compounds of cobalt, copper, palladium and nickel with polydentate ligands containing sulfur." Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4352.
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Ce travail porte sur la synthèse, la caractérisation et l’évaluation en catalyse de réduction des protons en dihydrogène, de nouveaux complexes de Ni(II), Co(III), Cu(II) et Pd(II) basés sur des ligands de type thiosemicarbazone. La nature de l’espèce catalytique active a été étudiée par voltampérométrie cyclique et des propositions de mécanisme ont été formulés sur la base de calcul quantique de type DFT.Le premier chapitre introduit le contexte scientifique. Le second chapitre concerne la synthèse et la caractérisation des ligands de type N2S2 et des complexes mononucléaires associés de Ni, Cu et Pd. Le troisième chapitre présente la synthèse et la caractérisation de complexes binucléaires de Co et trinucléaire de Ni.Les études électrochimiques de ces complexes dans le DMF en présence d’une source de protons, nous a permis d’évaluer leur efficacité catalytique. Nos résultats montrent que les complexes du Cu et du Pd présentent une vague irréversible spécifique pour la réduction des protons, mais une décomposition est observée durant l’électrolyse. Par contre, les complexes de Ni et de Co ont montré une stabilité électrochimique ainsi que de bonnes performances catalytiques. En particulier, le nouveau complexe mononucléaire de Ni présente des propriétés catalytiques remarquables qui le classent parmi les meilleurs catalyseurs de la réduction des protons décrits dans la littérature. L’ensemble de ce travail fourni une description complète du comportement électrochimique des ligands de type N2S2 complexés à des métaux de transition. Il permet d’envisager des développements futurs dans l’amélioration des propriétés catalytiques de ces complexesThis work focuses on the synthesis, the characterization and the catalytic evaluation in the reduction of protons into dihydrogen, of new complexes of Ni(II), Co(III), Cu(II) and Pd(II) based ligands Type thiosemicarbazone. The catalytically active species during the process of the proton reduction was studied by cyclic voltammetry and mechanisms were formulated on the basis quantum chemical calculation.The first chapter introduces the scientific context, the goals and the main objectives of this work. The second chapter concerns the synthesis and the characterization of the N2S2 ligands and their associated mononuclear complexes, Ni, Cu and Pd. The third chapter presents the synthesis and the characterization of binuclear Co and trinuclear Ni based on N2S2 ligand.Electrochemical studies of these complexes in DMF in the presence of a proton source (trifluoroacetic acid), allowed us to evaluate their catalytic efficiency. Our results show that Cu and Pd complexes have a specific irreversible wave for the reduction of protons, but decomposition is observed during electrolysis, which makes these uninteresting complexes for the reduction of protons.On the contrary, Ni and Co complexes showed an electrochemical stability and good catalytic performances. In particular, the new mononuclear Ni complex exhibits remarkable catalytic properties that rank it among the best catalysts for the reduction of protons reported in the literature. All this work provided a complete description of the electrochemical behavior of N2S2 thiosemicarbazone ligands complexed to transition metals. It allows considering future developments in improving the catalytic properties of these complexes
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Carson, Cantwell G. "Noble and transition metal aromatic frameworks synthesis, properties, and stability /." Diss., Atlanta, Ga. : Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/29657.
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Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2009.Committee Chair: Rina Tannenbaum; Committee Co-Chair: Rosario A. Gerhardt; Committee Member: E. Kent Barefield; Committee Member: Karl I. Jacob; Committee Member: Preet Singh; Committee Member: R. Bruce King. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Mayans, Ayats Júlia. "3d and/or 4f coordination compounds derived from chiral Schiff bases: magnetic and spectroscopic study." Doctoral thesis, Universitat de Barcelona, 2018. http://hdl.handle.net/10803/665178.
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This PhD thesis has been developed in the Molecular Magnetism Group of the University of Barcelona.
As its name indicates, the Molecular Magnetism Group is mostly interested in the magnetic study of coordination complexes, mainly with d metals but also with lanthanide cations, which permit magnetic studies but also luminescence studies, which could allow the syntheses of multifunctional products. The group has also interest in supramolecular chemistry and chirality.
The main objective of the thesis was the synthesis, magnetic and spectroscopic characterization of coordination complexes derived from chiral Schiff bases, used as organic ligands, and, due to the chirality of the organic ligands, the study of the chirality transfer from ligand to metal.
This series of organic ligands, have been combined with different metals: With 3d metals, like manganese, iron or nickel, but also with 4f metals or with combinations of both types. The metals used as paramagnetic cations have been used in the search of Single Molecule Magnet (SMM) behavior and also to develop a series of magnetostructural correlations. In other cases, the interesting part of the final product was related with their supramolecular chemistry.
All the products in this thesis have been magnetically characterized to try to elucidate their kind of magnetic interaction (ferromagnetic, antiferromagnetic or ferromagnetic), and, in the case that they present SMM behavior, to study their slow relaxation of the magnetization. Moreover, for complexes derived from lanthanide cations which are highly anisotropic due to the ion itself, other characterization techniques have been performed: Cantilever Torque Magnetometry (CTM) for the complete resolution of the magnetic anisotropy, and spectroscopic techniques like Electronic Paramagnetic Resonance (EPR), in X and W bands, in powder and monocrystal samples.
Due to the chiral nature of the used organic ligands, all the products in this thesis have been characterized by Electronic Circular Dichroism (ECD). This technique has been used to demonstrate the chirality of the products and the differences in the solution vs. solid structures.
The induced chirality in the final products due to the use of enantiopure reactants could allow the future study of the derived properties, like for example the emission of polarized light due to the presence of the lanthanide cation in a chiral environment, or the ferroelectricity, which should achieve the multiferrocity in the final materials.
The thesis contains a final chapter with a discussion about how the different ligands behaved with the different metals, about how the chirality of the reactants affected the final supramolecular structure, demonstrating that the chiral and racemic forms of a reactant not always yield in the same final structure, and about how the metals behave magnetically in each situation.L’objectiu principal de la tesi ha estat la síntesi i caracterització, magnètica i espectroscòpica, de complexes de coordinació derivats de bases de Schiff quirals. Les bases de Schiff han estat sintetitzades, o bé a partir d’una diamina condensada amb dos grups aldehid, o bé a partir d’un aminoalcohol condensat amb un grup aldehid. Aquesta sèrie de lligands orgànics, s’ha combinat amb diferents metalls, 3d¸4f o barreges dels dos. En d’altres casos, la part que ens ha interessat del complexes sintetitzats ha estat la seva química supramolecular. Tots els productes has estat caracteritzats magnèticament, per intentar esbrinar el seu tipus d’interacció magnètica (acoblament ferromagnètic, ferrimagnètic o antiferromagnètic) i, en cas de que presentessin propietats d’imant unimolecular, per esbrinar com era la seva relaxació magnètica. A més a més, per als compostos derivats de ions lantànid, que presenten una elevada anisotropia associada al catió, s’han dut a terme altres tècniques de caracterització magnètica, com l’anomenada Cantilever Torque Magnetomentry (CTM), i de caracterització espectroscòpica amb Ressonància Paramagnètica Electrònica (EPR) en banda X i en banda W, tan de compostos en pols com de monocristall. Degut a la naturalesa quiral dels lligands utilitzats, s’han pogut caracteritzar tots els productes mitjançant Dicroisme Circular Electrònic (ECD), que ens ha servit per demostrar tant la quiralitat dels productes com la seva estructura comparada en sòlid i en dissolució. La quiralitat induïda als productes mitjançant l’ús de reactius enentiomèricament purs, ha de permetre en el futur estudiar-ne les propietats que se’n deriven, com per exemple l’emissió de llum polaritzada deguda també a la presencia del catió lantànid, o la ferroelectricitat, que permetria aconseguir la síntesis de compostos multiferroics.
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Fuior, Arcadie. "Synthesis and characterization of coordination compounds based on [Mo2O2E2]2+ (E = O or S) fragments for applications in biology." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLV094.
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Ce travail porte sur la coordination des deux clusters polyoxomolybdate [Mo2O4]2+ et [Mo2O2S2]2+ avec divers ligands organiques et la recherche de leurs propriétés biologiques. Dans la première partie, des ligands chélatants simples et non toxiques tels que Ox, IDA, HNTA, EDTA, L-Cys et L-His sont liés à des centres [Mo2O2E2]2+ (E = O ou S) et sont étudiés en termes de stabilité chimique dans des solutions diluées et différents milieux aqueux pour une application ultérieure, notamment dans l’apiculture. Plusieurs complexes de molybdène se sont révélés être des compléments nutritionnels efficaces pour les abeilles Apis Mellifera. Par ailleurs, l'interaction des clusters [Mo2O2S2]2+ et ses complexes avec les cyclodextrines a été étudiée pour révéler des systèmes hôte-invité et des assemblages supramoléculaires intéressants. Dans la deuxième partie, 14 nouveaux composés de coordination dinucléaires à base de Mo2O2S2 avec des ligands organiques thiosemicarbazones sont décrits et leurs modes de coordination inusuels sont mis en évidence par des caractérisations à l’état solide et par des analyses extensives à l’état liquide (RMN 1H, 13C et 15N). Enfin, le potentiel pharmacologique de ces complexes est évalué sur des cellules cancéreuses du pancréas et du col utérin, des bactéries Gram positif et Gram négatif et des souches fongiques. La capacité antioxydante contre le radical cationique ABTS•+ est également évaluée. Les résultats montrent une bonne activité antitumorale in vitro et une très bonne action inhibitrice antibactérienne et antifongique dans la gamme micromolaire et des propriétés antioxydantes puissantes, permettant ainsi la formation de complexes de Mo(V) sous forme de molécules bioinorganiques multi-ciblesThis work focuses on the coordination of two particular polyoxomolybdate (POM) building blocks – [Mo2O4]2+ and [Mo2O2S2]2+ with various organic ligands and the investigation of their biological properties. In the first part, simple and non-toxic chelating ligands like Ox, IDA, HNTA, EDTA, L-Cys and L-His are linked to [Mo2O2E2]2+ cores and are studied in terms of chemical stability in diluted solutions and different aqueous media for further application, notably in beekeeping. Several molybdenum complexes have been found as efficient nutritional supplements for Apis Mellifera bees. Besides interaction of [Mo2O2S2]2+ clusters and complexes with cyclodextrins has been studied to reveal interesting host-guest systems and supramolecular assemblies.In the second part, 14 new binuclear Mo2O2S2-based coordination compounds with thiosemicarbazone organic ligands are reported and their particular coordination modes are evidenced through characterizations by solid-state and extensive liquid-state analyses (1H, 13C and 15N NMR). Finally the pharmacological potential of these complexes is evaluated on pancreatic and cervical cancer cells, Gram-positive and Gram-negative bacteria and fungal strains. Antioxidant capacity against ABTS•+ radical cation is assessed as well. The results show good in vitro antitumor activity and very good antibacterial and antifungal inhibition action in the micromolar range and powerful antioxidant properties, therefore enabling the formation of POM-based Mo(V) complexes as multi-target bioinorganic molecules
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Adams, Julian James. "A C₂-symmetric analogue of dppf : synthesis and characterization of indenyl-phosphines, phosphino-ferroindacenes and their coordination compounds." Thesis, University of Canterbury. Chemistry, 1998. http://hdl.handle.net/10092/7564.
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The synthesis, isolation and characterisation of a series of indenyl phosphines: 3-diphenylphosphinoindene (ppinH), 1,3- bis(diphenylphosphino)indene (dppinH), bis(3-indenyl)phenylphosphine (pdinH₂) and tris(3-indenyl)phosphine (ptinH₃) is reported. Until now these compounds have been either uncharacterized or poorly characterized in the literature. The reactions of ppin-, dppin- and pdin²- with ferrous chloride were investigated. Fe(ppin)₂ exists in two isomeric forms: a racemic isomer with C₂ symmetry and a meso form with C₂ symmetry, these are analogues of dppf. Crystallographic investigations of the coordination compounds of Fe(ppin)₂ allowed isolation of both isomers of the Fe(ppin)₂Mo(CO)₄ complex, and the meso isomer of the Fe(ppin)₂PdCb complex. Solution NMR investigations of Fe(ppin)₂PdCl₂ and Fe(ppin)2PtCl₂ show two compounds in solution in each case, suggesting a dynamic process. The electrochemistry of the complexed and uncomplexed ferroindacene show reversible oxidation processes in dry dichloromethane at E½ = -140 mV (Fe(ppin)₂), +60 mV (Fe(ppin)₂Mo(CO)₄) and +260 mV (Fe(ppin)₂PdCl₂) vs. Fe/Fc+. The investigation of the tetraphosphinoferroindacene Fe(dppin)₂ showed it only to be stable in dilute solution and that the major decomposition product is Fe(ppin)₂. The decomposition mechanism is unknown. The synthesis of diferrocenobis(phenylphosphino)cyclophane, an eight membered diferrocenlycyclophane characterized by mass spec and NMR, is described and the investigation of the indenyl analogue of diferrocenobis(phenylphosphino)cyclophane Fe₂(pdin)₂ which proved to be very unstable, is also described.
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Kleinhans, Dewald Johannes. "Studies in the selective synthesis of bidentate resorcinarene ligands." Thesis, Stellenbosch : University of Stellenbosch, 2010. http://hdl.handle.net/10019.1/4194.
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Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010.ENGLISH ABSTRACT: Resorcinarenes are macrocyclic products formed from the condensation of aldehydes (aliphatic or aromatic) and resorcinol and have been used in a wide range of applications since their first synthesis. Applications include: HPLC stationary phases for the separation of pyrimidine bases, racemic drugs and isomers, the selective extractions of lanthanides and actinides, as molecular receptors, catalysis, NMR chiral shift agents, GC separations and as starting materials for the synthesis of macrocyclic compounds (e.g. cavitands and carcerands) to name but a few. The use of resorcinarenes in catalysis is still quite new and unexplored, while catalysis using calix[4]arenes, a related macrocycle, has been widely studied. In this thesis it was attempted to synthesise a C2v symmetric resorcinarene precursor that could be further functionalised to form distal bidentate ligands for coordination to transition metals. These compounds would then ultimately be used in catalytic testing, especially for Pd catalysed C-C bond formation. A dibromo resorcinarene precursor was synthesised starting from resorcinarene, using methodology developed by Shivanyuk. This molecule was functionalised with a small range of different electrophiles using lithium halogen exchange methodology, although low yields were returned for the expected distal resorcinarene compounds. Other methods of functionalisation of the resorcinarene, using an anionic ortho-Fries rearrangement and the reduction of a dinitrile resorcinarene to amine and aldehyde functionalities proved unsuccessful. Using a dithioether resorcinarene a di-nuclear coordination compound was formed with Pd(II). This compound was tested for catalytic activity with a Heck reaction, showing low yields for the coupling of styrene with bromobenzene.
AFRIKAANSE OPSOMMING: Resorsinarene is makrosikliese produkte wat gevorm word deur die kondensasie van aldehiede (alifaties of aromaties) met resorsinol en word in ‘n verskeidenheid van toepassings gebruik sedert hulle eerste sintese. Tipiese voorbeelde sluit in: stationêre fases vir die HPLC-skeiding van pirimidien-basisse, rasemiese farmaseutiese middels en isomere, die selektiwe ekstraksie van lantaniede en aktiniede, molekulêre reseptore, katalise, chirale verskuiwingsreagense vir KMR spektrometrie, GC-skeidings en as uitgangverbindings vir die sintese van ander makrosikliese verbindings (bv. kavitande en karserande). Die gebruik van resorsinarene in katalise is ’n splinternuwe onontginde veld. In teenstelling hiermee is calix[4]areen, ’n verwante makrosikliese verbinding, baie meer bestudeer en vir katalise gebruik. Die doel van hierdie tesis was om ’n C2v simmetriese uitgangstof te sintetiseer wat verder gefunksionaliseer kan word om distale, bidentate ligande vir koordinasie met oorgangsmetale te lewer. Daar is beplan om die katalitiese eienskappe van die komplekse te toets, veral vir Pd-gekataliseerde C–C-koppelings reaksies. Deur gebruik te maak van ’n protokol wat deur Shivanyuk ontwikkel is, is ’n dibromo-resorsinareen gesintetiseer uit resorsinareen. Verskillende elektrofiele is in ’n litium-halogeen uitruilreaksie gebruik om ’n beperkte verskeidenheid nuwe ligande te sintetiseer wat verskillende funksionele groepe besit. Ongelukkig was die opbrengste aan distale ligande baie laag en ander metodes is dus ook ondersoek om die funksionalisering te bewerkstellig. ’n Anioniese orto-Fries herrangskikkingsreaksie en die reduksie van ’n dinitriel-resorsinareen om amien- en aldehiedfunksies te lewer, was ook onsuksesvol. Die reaksie tussen ‘n Pd(II) sout en ‘n ditioeter-gederivatiseerde resorsinareen het ‘n koordinasie verbinding met twee metaalkerne gelewer. Hierdie kompleks is deur middel van ‘n Heck-koppelingsreaksie vir katalitiese aktiwiteit getoets, maar het lae opbrengste gelewer in die koppeling van stireen en bromobenseen.
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Fellows, Simon Matthew. "Novel copper coordination compounds of amino acids and pyridines : synthesis, characterisation, physical properties, and future prospects for gas adsorption." Thesis, University of Hull, 2017. http://hydra.hull.ac.uk/resources/hull:16896.
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The primary goal of the work discussed in this thesis was to assess the capability of cheap, readily available ligands, e.g. pyridines and amines, to produce new coordination compounds, primarily with copper, that could lead to the development of novel materials for gas adsorption. Chapters 1 and 2 introduce the topic and methods respectively, results are contained within chapters 3-6. Chapter 3 describes the synthesis, polymorphism and solid-gas reactions of [CuCl₂(RPy)₂] and (RPy-H)[CuCl₄] (RPy: R = 4-CO₂H, 4-CONH₂, 3-CONH₂). The polymeric [CuCl₂(RPy)₂] compounds appear blue, while the equivalent (RPy-H)[CuCl₄] salts appear yellow or green depending on the geometry of the [CuCl₄]²⁻ ion. Exchange between the two types of compound is possible through the gain and loss of HCl, although the exact mechanism and what causes the observed differences in reaction is uncertain. [CuCl₂(RPy)₂] compounds could be developed further into porous materials through the use of simple tris(pyridine) ligands. Chapter 4 discusses a facile synthetic method for [Cu₄(μ⁴-O)(μ²-Cl)6(RPy)₄] compounds via the oxidation of CuCl in the presence of [CuCl₂(RPy)₂]n (RPy: R = 4-Me, 4-NH₂, 4-NMe₂). The production of the [Cu₄(μ⁴-O)(μ²-Cl)6(RPy)₄] cluster only seems to occur for compounds where the [CuCl₂(RPy)₂] complex is non-polymeric or at least weakly polymeric. Only one porous [Cu₄(μ⁴-O)(μ²-Cl)6(RPy)₄] compound is known with 1,4-diazabicyclo[2.2.2]octane, but there is potential for others to be discovered. However, these compounds are not as stable as other compounds that might be used for gas adsorption and are better suited for catalysis applications. Chapter 5 focuses on the copper and zinc coordination chemistry of amino acids with general formula CO₂H-(CH₂)n-NH₂ (where n = 1-5 and 7). Amino acids are a good potential ligand for CO₂ capture given their similarity with monoethanolamine: the most common chemical used in industrial technologies. However, their flexibility and propensity to form zwitterions means that the majority of compounds produced were adducts of copper halides, and those which were not appeared too dense for application in CO₂ adsorption. The copper halide adducts showed similar HCl/HBr gas uptake as the [CuCl₂(RPy)₂] compounds in chapter 3, although the reverse reaction was much slower with very little change observed over several months. Lastly, chapter 6 details the novel coordination compounds created using Cu and a combination of various benzoic acid based and pyridine-based ligands. Most of the novel compounds have only been structurally characterised and no general conclusions can be made about their structures due to the lack of data. One compound made with 4-hydroxybenzoic acid and pyrazine in methanol showed promise for methanol adsorption, however the compound could not be made reliably or quantities large enough to study the phenomenon further.
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Brodsky, Kathy-Jo. "The synthesis and characterization of bis(4-(3-(4-phenoxy)propionitrile))-N, N-disalicylidene-1,2-phenylenediamino)zirconium(IV), Zr(nitrile)₂ and the attempted synthesis of Zr(amine)₂ and coordination polymers containing Zr(dspOH)₂ /." Online version of thesis, 1994. http://hdl.handle.net/1850/11764.
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Rajnak, Cyril. "Synthesis of spin transition compounds for surface deposition." Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAE040.
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Cette thèse de doctorat présente les résultats d'une étude expérimentale des composés à transition de spin pour le dépôt de surface. Nous nous sommes concentrés sur Fe(II) systèmes avec la configuration de d6 et leur comportement bistable ST. Dans une symétrie octaédrique le configuration d6 peut adopter deux états fondamentaux électronique différentes selon l'occupation des orbitales d scindé en exemple eg et t2g sous-ensembles. Si la différence d'énergie entre deux états est petite, alors tourner transition peut être induite par un stimulus externe. En fait, les complexes adoptent l'état haut spin ou l'état bas spin en raison de la différence d'énergie entre les orbitales (eg, t2g) et de l'énergie de répulsion interélectronique. Nous avons synthétisé et caractérisé de nouveaux ligands tridentates organiques, qui ont été utilisés comme précurseurs pour les nouveaux Fe(II) composés de coordination. Nous avons préparé des complexes Fe(II) avec et sans contre-anionsThis doctoral thesis presents the results of an experimental study of the spin transition compounds for surface deposition. We have focused on Fe(II) systems with d6 configuration and their bistable ST behaviour. In an octahedral symmetry the d6 configuration can adopt two different electronic ground states according to the occupation of the d orbitals split into the eg and t2g subsets. If the energy difference between two states is small then the spin transition can be induced by an external stimulus. In fact, the complexes adopt the high-spin state or the low-spin state by reason of energy difference between orbitals and interelectronic repulsion energy. Nine novel tridentate ligands have been synthesized and characterized; they were used as precursors for new Fe(II) coordination compounds. The SQUID magnetometry was used in studying magnetic properties of prepared complexes and the XAS technique was also applied to study magnetic properties of a neutral complex on an adhesive graphite tape
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Costa, Wijeendra M. R. S. "Coordination of Chemistry of Re(I) Carbonyl Complexes as Pharmaceutically Important Compounds and Synthesis, Characterization, and Metalation of Novel Phthalocyanine Analogs." University of Akron / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=akron1302492223.
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Pryor, Donald Edward. "Synthesis and Bioactivity Studies of Nanoparticles Based on Simple Inorganic and Coordination Gallium Compounds as Cellular Delivering Vehicles of Ga(III) Ions for Potential Therapeutic Applications." Kent State University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=kent1543554532063877.
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Ivy, Joshua F. "Optoelectronically Active Metal-Inorganic Frameworks and Supramolecular Extended Solids." Thesis, University of North Texas, 2018. https://digital.library.unt.edu/ark:/67531/metadc1248495/.
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Metal-organic frameworks (MOFs) have been intensely researched over the past 20 years. In this dissertation, metal-inorganic frameworks (MIFs), a new class of porous and nonporous materials using inorganic complexes as linkers, in lieu of traditional organic linkers in MOFs is reported. Besides novel MIF regimes, the previously described fluorous MOF "FMOF-1", is re-categorized herein as "F-MIF1". F-MIF-1 is comprised of [Ag4Tz6]2- (Tz = 3,5-bis-trifluoromethyl-1,2,4-triazolate) inorganic clusters connected by 3-coordinate Ag+ metal centers. Chapter 2 describes isosteric heat of adsorption studies of F-MIF1 for CO2 at near ambient temperatures, suggesting promise for carbon capture and storage. We then successfully exchanged some of these Ag(I) centers with Au(I) to form an isostructural Au/F-MIF1. Other, nonporous MIFs have been synthesized using Ag2Tz2 clusters with bridging diamine linkers 4,4'-bipyridine, pyrazine, and a Pt(II) complex containing two oppositely-situated non-coordinating pyridines. This strategy attained luminescent products better-positioned for photonic devices than porous materials due to greater exciton density.
Chapter 3 overviews work using an entirely inorganic luminescent complex, [Pt2(P2O5)4]4- (a.k.a. "PtPOP") to form new carbon-free MIFs. PtPOP is highly luminescent in solution, but as a solid shows poor quantum yield (QY ~0.02) and poor stability under ambient conditions. By complexing PtPOP to various metals, we have shown a dramatic enhancement in its solid-state luminescence (by an order of magnitude) and stability (from day to year scale). One embodiment (MIF-1) demonstrates microporous character.
Chapter 4 overviews the design and application of new MIF linkers. Pt complexes based upon (pyridyl)azolates, functionalized with carboxylic acid groups, have been synthesized. These complexes, and their esterized precursors, show strong luminescence on their own. They have been used to generate new luminescent MIFs. Such new MIFs may be useful toward future inorganic (LEDs) or organic (OLEDs) light-emitting diodes, respectively. The electronic communication along their infinite coordination structures is desirable for color tuning and enhanced conductivity functions, compared to the small molecules used in such technologies, which rely on intermolecular interactions for these functions.
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Gallen, Ortiz Albert. "P-Stereogenic ligands with the tert-butylmethylphosphine fragment. Coordination chemistry and catalysis of their organometallic complexes." Doctoral thesis, Universitat de Barcelona, 2019. http://hdl.handle.net/10803/666577.
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The Thesis deals with the preparation, coordination chemistry and use in asymmetric homogeneous catalysis of several optically pure P-stereogenic ligands containing a tert-butylmethylphosphino fragment.
In the first part a highly stereoselective synthesis of the Secondary Phosphine Oxide (SPO) tert-butylmethylphosphine oxide is presented. Despite its simplicity, the stereoselective synthesis of this SPO had not been described in the literature. It is known that SPOs present a tautomeric equilibrium between the air-stable pentavalent form (phosphine oxide) and the trivalent form (phosphinous acid), usually completely shifted towards the pentavalent form but that can be displaced towards the phosphinous acid form by metal complexation. In the Thesis the complexation of the mentioned oxide towards Ru, Rh, Ir, Ni, Pd and Au has been explored, yielding a variety of coordination and organometallic compounds, with several coordination modes of the ligand. Some asymmetric catalytic applications of these species have also been studied, giving good conversions but low enantioselectivities.
In the second part of the Thesis, the C1-symmetric P-stereogenic ligand MaxPhos has been coordinated to [MCp*Cl] (M = Rh and Ir) and [Ru(p-cymene)Cl] fragments, yielding cationic M-stereogenic organometallic compounds as tetrafluoroborate or hexafluorophosphate salts. Interestingly, in all cases a single stereoisomer has been formed, as confirmed by NMR and X-ray crystallography. This has been rationalised by steric grounds. For Ir, the abstraction of the remaining chloride ligand by silver salts produced a diastereoselective C–H activation of a tert-butyl group of the ligand. The complexes have been used in transfer hydrogenation giving good activities but no enantioselectivities.
Finally the third part of the Thesis is devoted to the cyclometallation of [Ir(MaxPHOX)COD]BArF complexes (MaxPHOX stands for a type of P,N phosphinooxazoline ligand recently described by our group having three stereogenic centres) by several ligands under hydrogen atmosphere. It has been found that cyclometallated Ir(III)-hydrido complexes are formed, which are very stable and have been characterised thoroughly. They have been used in asymmetric hydrogenation of N-alkylimines, giving in general complete conversions and very high enantioselectivities (up to 96% ee) for these substrates, which rank among the best described to date. The mechanism of the reaction has been studied and the stereochemical outcome rationalised by means of DFT-based computational methods.La Tesi presenta la preparació, coordinació i ús en catàlisi homogènia asimètrica d’una varietat de lligands P-estereogènics òpticament purs que contenen el grup tert- butimetilfosfina. A la primera part es presenta la síntesi, altament estereoselectiva, de l’òxid de fosfina secundari (SPO) òxid de tert-butilmetilfosfina. Malgrat la simplicitat d’aquest compost, no se n’havia descrit la síntesi de forma estereoselectiva a la bibliografia. Se sap que els SPOs presenten un equilibri tautomèric entre la forma pentavalent estable a l’aire (òxid de fosfina) i la forma trivalent (àcid fosfinós). Habitualment aquest equilibri es troba totalment desplaçat envers la forma pentavalent però es pot desplaçar cap a l’àcid fosfinós per complexació amb un metall. A la Tesi, s’ha estudiat la complexació de l’òxid esmentat a Ru, Rh, Ir, Ni, Pd i Au i ha donat una gran varietat de compostos de coordinació i organometàl·lics, en els quals el lligand presenta una varietat de modes coordinació. També s’han explorat algunes aplicacions catalítiques d’aquestes espècies i s’han trobat bones conversions però baixes enantioselectivitats. A la segona part de la Tesi el lligand P-estereogènic de simetria C1 MaxPhos s’ha coordinat a fragments [MCp*Cl] (M = Rh o Ir) i [Ru(p-cimè)Cl] i ha donat compostos organometàl·lics catiònics M-estereogènics en forma de sals de tretrafluoroborat o hexafluorofosfat. És interessant destacar que estudis de RMN i cristal·lografia de raigs X han demostrat que en tots els casos s’ha format un sol estereoisòmer, fet que s’ha racionalitzat per arguments estèrics. En el cas del Ir, la abstracció del lligand cloruro amb sals de plata ha provocat l’activació de l’enllaç C–H d’un grup tert-butil de lligand en forma diastereoselectiva. Tots els compostos preparats s’han utilitzat en transferència d’hidrogen asimètrica i han donat bones activitats però enantioselectivitats baixes. Finalment, la tercera part de la Tesi està dedicada a la ciclometal·lació de complexos [Ir(MaxPHOX)COD)BArF amb diferents lligands auxiliars sota atmosfera d’hidrogen, on MaxPHOX és un lligand P,N de tipus fosfinooxazolina que el nostre grup de recerca ha descrit recentment i que conté tres centres estereogènics. S’ha observat la formació de complexos ciclometal·lats Ir(III)-hidrur molt estables, que s’han caracteritzat exhaustivament. Aquests complexos s’han usat com a catalitzadors per la reacció d’hidrogenació asimètrica d’imines alquíliques i ha donat conversions completes i enantioselectivitats de fins el 96% d’ee, que es troben entre els millors que s’han descrit mai per a aquests tipus de substrats. S’ha estudiat el mecanisme de la reacció i el curs estereoquímic, que s’ha racionalitzat mitjançant mètodes computacionals de tipus DFT.
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MENDES, MARIA ROSANGELA DE VASCONCELOS. "SYNTHESIS, CHARACTERIZATION AND SPECTROSCOPIC STUDY ON A NEW LIGAND DERIVED FROM BARBITURIC ACID AND ISONIAZID AND ITS COORDINATION COMPOUNDS WITH THE TRANSITION METAL IONS ZN(II) AND CU(II)." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2016. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=32444@1.
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PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIROCOORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO
O presente trabalho trata da síntese, caracterização e estudo espectroscópico de novo ligante derivado da reação do ácido barbitúrico e isoniazida e seus respectivos complexos de zinco e cobre que foram todos igualmente estudados. Foi proposto um roteiro de síntese em meio aquoso utilizando metodologia gráfica para delinear as melhores condições de obtenção dos produtos. Um estudo espectroscópico completo dos reagentes foi realizado para ajudar na caracterização do ligante e dos complexos. A interpretação dos espectros de infravermelho e Raman foi acompanhada com os cálculos mecânico-quânticos utilizando o método DFT/B3LYP e o conjunto de base 3-21G acompanhado com os dados experimentais obtidos pela análise da segunda derivada do espectro. Os espectros de infravermelho com transformada de Fourier, e Raman tendo como base a estrutura proposta de acordo com os dados de CHN, RMN e absorção atômica, apresentaram uma excelente concordância com os espetros experimentais. A baixa solubilidade do ácido barbitúrico e seus derivados em regiões de pH acima de 5 produz uma mistura de hidroxo-complexos que dificulta o estudo das regiões de baixa energia, onde os modos vibracionais metal-ligante ocorrem. A metodologia gráfica empregada permitiu a obtenção de produtos mais puros e cristalizados possibilitando a correta caracterização espectroscópica de todos os modos vibracionais.
The present study examined the synthesis, characterization, and spectroscopic study of new ligand derived from the reaction of barbituric acid and isoniazid. The ligand was used to synthetize complexes of zinc and copper and these complexes were analyzed. A synthesis plan was proposed in an aqueous medium using a graphical methodology, ensuring the best conditions to obtain the products. A complete spectroscopic study of reagents was implemented to aid in the characterization of both the ligand and the complexes. The interpretation of infrared spectra and Raman was complemented with a quantum-mechanical calculation method using DFT / B3LYP and a 3-21G basis. These calculations were compared with experimental data obtained by analyzing the second derivative of the spectrum. Based on the structure proposed according to the data of CHN, NMR, and the atomic absorption; the infrared spectra with a transformed Fourier and Raman were in line with the experimental spectra. Lastly, these conclusions lead us to better understand the complexities in spectroscopic characterization of compounds derived from barbituric acid and its coordination compounds. The low solubility of barbituric acid and its derivatives in pH regions above 5 creates a mixture of hydroxide complexes which complicate the study of low energy regions, where the metal-ligand vibrational modes occur. The graphical methodology used allowed us to obtain purer crystallized products, enabling the correct spectroscopic characterization of all vibrational modes.
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Höhne, Dominik [Verfasser], Fritz Elmar [Akademischer Betreuer] Kühn, and Kai-Olaf [Akademischer Betreuer] Hinrichsen. "Synthesis and Characterization of Dicarboxylate-bridged and Bisphosphine-substituted Dimolybdenum(II) Complexes as Potential Building Blocks for Supramolecular Coordination Compounds / Dominik Höhne. Betreuer: Fritz Elmar Kühn. Gutachter: Fritz Elmar Kühn ; Kai-Olaf Hinrichsen." München : Universitätsbibliothek der TU München, 2015. http://d-nb.info/1078420610/34.
Full text
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Daire, Fabrice. "Etude d'electrodes modifiees par fixation de composes de coordination sur un support conducteur du type polypyrrole : application en electrosynthese organique." Paris 6, 1988. http://www.theses.fr/1988PA066176.
Full textAbstract:
Proprietes electrochimiques des complexes co-l, cu-l, ni-l (ou l=methyl-4, bipyridine-2,2', derive du pyrrole) dans l'acetonitrile. Polymerisation electrolytique de ces complexes sur des electrodes d'or, platine et carbone. Proprietes electrochimiques du polymere co-bipyridyl-polypyrrole; utilisation dans la reduction catalytique des derives allyliques
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Al-Harbi, Ahmed Baker. "Synthesis and Coordination Chemistry of Oxygen Rich Ligands: Bis(oxoimidazolyl)hydroborato, Tris(oxoimidazolyl)hydroborato and Tris(2-pyridonyl)methane." Thesis, 2014. https://doi.org/10.7916/D85Q4T42.
Full textAbstract:
In Chapter One, the sodium salt of tris (2-oxo-1-t-butylimidazolyl) hydroborate, [To^But]Na, as an [O_3] donor ligand has been prepared. The yield for this reaction was low because there is a significant amount of side product in which the double bond of the oxoimidazole starting material is reduced. Treatment of sodium borohydride with bezannulated oxoimidazole at high temperature leads to the generation of the sodium salt of tris (2-oxo-1-R-methylbenimidazolyl) hydroborate in high yield, [To^RBenz]Na. These ligands have been prepared with different alkyl substituents, methyl, t-butyl and adamantyl, to achieve the desired steric environment. Furthermore, these benzannulated ligand have been used to synthesize a series [To^RBenz]Tl complexes, which exist as a discrete mononuclear complexes in the solid state. Finally, [To^RBenz]Tl complexes are more pyramidal than the sulfur counterpart, [Tm^RBenz]Tl, but less pyramidal than those in the tris (pyrazolyl)hydroborato counterpart, [Tp^R,R]]Tl.
In Chapter Two, the properties of [To^R] ligands have been evaluated versus related L_2X ligands. [To^R] ligands are substantially more sterically demanding than the corresponding [Tm^R] sulfur donor ligand and related [O_3] donor ligands. However, electronically, the [To^R] ligands exhibit weaker electron donating properties than other L_2X type ligands. Finally, the coordination chemistry of [To^R] ligands with various metal compounds has been briefly investigated. The synthesis of a new class of bidentate ligands has been detailed in Chapter Three. Namely the bis(2-oxo-1-t-butylimidazolyl)hydroborato and bis (2-oxo-1-alkylbenzimidazolyl)hydroborato, [Bo^But] and [Bo^RBenz], have been synthesized via the reaction of MBH_4 with two equivalents of the respective 2-imidazolone. Chelation of [Bo^But] and [Bo^MeBenz] to a metal center results in a flexible 8-membered ring that is capable of adopting a "boat-like" conformation that allows for secondary M—H—B interactions. Chapter Four describes the synthesis of [Bo^RBenz]_2Zr(CH_2Ph)_2and [To^RBenz]Zr(CH_2Ph)_3 with different alkyl substituents. Treatment of [To^ButBenz]Zr(CH_2Ph)_3 with ([PhNHMe_2][B{C_6F_5}_4]) in a coordinating solvent, Et_2O, generates {[To^ButBenz]Zr(CH2Ph)_2(OEt_2)}{B(C_6F_5)_4} which exhibit a very low activity for ethylene polymerization. However, a coordinatively unsaturated cationic zirconium alkyl complex was obtained by the treatment of ([PhNHMe_2][B{C_6F_5}_4]) with [To^ButBenz]Zr(CH_2Ph)_3 or [To^AdBenz]Zr(CH_2Ph)_3 which generate [To^ButBenz]Zr(CH_2Ph)_2[B(C_6F_5)_4 or [To^AdBenz]Zr(CH_2Ph)_2[B(C_6F_5)_4], respectively. Moderate activity for ethylene polymerization was obtained for t-butyl while high activity was obtained for the adamantyl derivatives. Finally, Chapter Five describes the synthesis of new oxygen-rich ligands, namely tris (2-pyridonyl)methane, [Tpom^R]H. They are obtained via the reaction of 2-pyridones with CHX_3 and K_2CO_3 in the presence of [Bu^n _4N]Br, followed by acid-catalyzed isomerization with camphorsulfonic acid. These compounds provide access to a new class of L_3X alkyl ligands that feature oxygen donors and are capable of forming metallacarbatranes, as exemplified by [Κ^4-Tpom^But]ZnOC6H4Bu^t. In addition, the [Tpom^But] ligand also allows isolation of a monovalent thallium alkyl compound, [Tpom^But]Tl, in which the Tl—C bond is long and has little covalent character.
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"Synthesis, structure, and weakly coordinating nature of new carborane anions." 2000. http://library.cuhk.edu.hk/record=b6073267.
Full textAbstract:
Chi-wing Tsang."July 2000."
Thesis (Ph.D.)--Chinese University of Hong Kong, 2000.
Includes bibliographical references (p. 151-160).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Mode of access: World Wide Web.
Abstracts in English and Chinese.
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"Synthesis and characterization of b-substituted porphyrins and their metal complexes: Monomer, Dimer and coordination polymer." Chinese University of Hong Kong, 1996. http://library.cuhk.edu.hk/record=b5895715.
Full textAbstract:
by Xiang Zhou.Thesis (Ph.D.)--Chinese University of Hong Kong, 1996.
Includes bibliographical references.
Acknowledgment --- p.i
Abstract --- p.ii
Abbreviations --- p.iii
Table of Contents --- p.iv-v
Chapter Chapter I --- Synthesis of β-substituted porphyrins --- p.1
Chapter I-1 --- Introduction --- p.1
Chapter I-1-1 --- Activation of alkanes: the biomimetic approach --- p.2
Chapter I-1-2 --- Electronic effects in β-substituted porphyrins --- p.5
Chapter I-1-3 --- Synthetic approach to β-substituted porphyrins --- p.7
Chapter I-2 --- Results and discussions --- p.14
Chapter I-2-1 --- Bromination of porphyrins at β-positions --- p.14
Chapter I-2-2 --- Synthesis of boronic acids --- p.17
Chapter I-2-3 --- Synthesis of β-substituted porphyrins --- p.18
Chapter I-2-4 --- Uv spectra --- p.25
Chapter I-2-5 --- "Crystal structures of H2TPP(Ph)4, H2TPP(Me)4， H2TPP(Tol)8 and H2TMP(Ph)8" --- p.26
Chapter I-3 --- Conclusion --- p.43
Chapter I-4 --- Experimental section --- p.44
Chapter I-5 --- References --- p.58
Chapter Chapter II --- Synthesis and Properties of Diporphyrins --- p.63
Chapter II-1 --- Introduction --- p.63
Chapter II-1-1 --- Linear dimers --- p.64
Chapter II-1-2 --- Cofacial porphyrins (or strati-bisporphyrins) --- p.68
Chapter II-1-3 --- Synthetic approach --- p.71
Chapter II-2 --- Results and discussions --- p.73
Chapter II-2-1 --- Synthetic strategy --- p.73
Chapter II-2-2 --- Synthesis of diporphyrins via condensation and Suzuki cross- coupling --- p.75
Chapter II-2-3 --- Synthesis of diporphyrins via Suzuki cross-coupling and condensation --- p.75
Chapter II-2-4 --- Metalation of diporphyrins --- p.78
Chapter II-2-5 --- Spectroscopy --- p.81
Chapter II-3 --- Conclusion --- p.89
Chapter II-4 --- Experimental section --- p.90
Chapter II-5 --- Reference --- p.100
Chapter Chapter III --- Novel Rhodium Porphyrin Complexes: Intermolecular Activation of Arene Carbon-Hydrogen Bond and Formation of a Nitrile-Bridged Coordination Polymer --- p.104
Chapter III-l --- Introduction --- p.104
Chapter III-1-1 --- Activation of C-H bonds --- p.104
Chapter III-1-2 --- Activation of C-H bond by rhodium porphyrin complexs --- p.106
Chapter III-2 --- Results and discussions --- p.108
Chapter III-2-1 --- Synthesis of rhodium porphyrin complexes --- p.108
Chapter III-2-2 --- Proton NMR --- p.112
Chapter III-2-3 --- UV and binding studies of rhodium porphyrin complexes --- p.115
Chapter III-2-4 --- IR spectra --- p.117
Chapter III-2-5 --- Crystal structures of rhodium porphyrin complexes --- p.118
Chapter III-3 --- Conclusion --- p.148
Chapter III-4 --- Experimental section --- p.149
Chapter III-5 --- References --- p.154
Appendix --- p.157
NMR Spectra --- p.159
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"Generation of coordination polymeric structures by dicarboxylate-like ligands." Chinese University of Hong Kong, 1996. http://library.cuhk.edu.hk/record=b5888863.
Full textAbstract:
by De-Dong Wu.Publication date from spine.
Thesis (Ph.D.)--Chinese University of Hong Kong, 1995.
Includes bibliographical references (leaves 175-184).
Acknowledgment --- p.i
Abstract --- p.ii
Table of Contents --- p.iii
List of Tables --- p.iv
List of Figures --- p.v
Chapter 1. --- Introduction --- p.1
Chapter 1.1. --- The Chemistry of Coordination Polymers --- p.1
Chapter 1.2. --- Generation of Coordination Polymeric Structures --- p.2
Chapter 1.3. --- Research Strategy --- p.7
Chapter 2. --- Description of Crystal Structures --- p.15
Chapter 2.1. --- The Double Betaine Compounds --- p.15
Chapter 2.2. --- Complexes of Silver(I) --- p.39
Chapter 2.3. --- Complexes of Cadmium(II) --- p.60
Chapter 2.4. --- Complexes of Mercury(II) --- p.89
Chapter 2.5. --- Complexes of Copper(II) and Sodium(I) --- p.113
Chapter 3. --- Summary and Discussion --- p.127
Chapter 3.1. --- Generation of Coordination Polymeric Structures --- p.127
Chapter 3.2. --- Coordination Modes of Double Betaines --- p.132
Chapter 3.3. --- Conformation of the Double Betaines --- p.135
Chapter 3.4. --- Synthesis of Betaine Compounds --- p.139
Chapter 4. --- Experimental --- p.150
Chapter 4.1. --- Preparation --- p.150
Chapter 4.2. --- Physical Measurements --- p.164
Chapter 4.3. --- Crystallography --- p.164
Chapter 5. --- References --- p.175
Appendix --- p.185
Chapter 1. --- Atomic coordinates and equivalent isotropic thermal parameters --- p.185
Chapter 2. --- Anisotropic thermal parameters --- p.196
Chapter 3. --- H-atom coordinates and isotropic thermal parameters --- p.203
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"Part I. Coordination chemistry of SmI3 with donor solvents: Part II. Synthesis and structural characterization of lanthanacarboranes." 1997. http://library.cuhk.edu.hk/record=b5889217.
Full textAbstract:
by Ka-yue Chiu.The "3" in the title is subscript.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1996.
Includes bibliographical references (leaves 103-110).
ACKNOWLEDGEMENTS --- p.3
ABBREVIATIONS --- p.4
ABSTRACT --- p.5
Chapter I. --- COORDINATION CHEMISTRY OF SmI3 WITH DONOR SOLVENTS --- p.7
Chapter 1.1. --- Introduction --- p.7
Chapter 1.2 --- Results and Discussion --- p.21
Chapter 1.2.A --- Synthesis and Structural Characterization of [trans-SmI2(THF)5][trans- SmI4(THF)2] (1) --- p.21
Chapter 1.2.B --- Synthesis and Structural Characterization of SmI3(DME)2 (2) --- p.26
Chapter 1.2.C --- Synthesis and Structural Characterization of [{Sm(H20)3}2{Sm(CH3CN) (H20)3}2{Sm(CH3CN)3(H20)}2(μ3-OH)8(μ6-0)]I8-2H20 (3) --- p.30
Chapter 1.3 --- Conclusion --- p.38
Chapter 1.4 --- Experimental Section --- p.39
Chapter II. --- SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF LANTHANACARBORANES --- p.45
Chapter II.1 --- Introduction --- p.45
Chapter II.2 --- Results and Discussion --- p.51
Chapter II.2.A --- Synthesis and Characterization of closo-Lanthanacarboranes --- p.51
Chapter II.2.A.i --- Sandwich Type Complexes --- p.51
Chapter II.2.A.ii. --- Half-Sandwich Type Complexes --- p.62
Chapter II.2.B --- Synthesis and Characterization of an exo-nido-Samaracarborane --- p.71
Chapter II.2.B.i. --- Synthesis and Characterization of an exo-nido-[{(C6H5CH2)2C2B9H9} Sm(DME)2]2.DME(18) --- p.77
Chapter II.3 --- Conclusion --- p.84
Chapter II.4 --- Experimental Section --- p.85
REFERENCES --- p.99