Dissertations / Theses: 'Cobalt(II) coordination polymer'

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James, Christopher Dominic. "PARAMAGNETIC RESONANCE STUDIES OF HIGH-SPIN COBALT (II) COORDINATION COMPLEXES." Miami University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=miami152267342524459.

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Altahan, Mohammed Abdulredha. "Cobalt(III), copper(II), and nickel(II) coordination compounds as cations in polyborate chemistry." Thesis, Bangor University, 2017. https://research.bangor.ac.uk/portal/en/theses/cobaltiii-copperii-and-nickelii-coordination-comppounds-as-cations-in-polyborate-chemistry(ba5f189b-2229-481f-9d8d-0bdce17903a8).html.

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This thesis describes the synthesis and characterization of a number of polyborate compounds containing transition metal complex cations; most of these compounds contain 6-membered B3O3 boroxole rings within their structures. A total of twenty-six transition metal complex polyborate salts are reported: one contains the triborate monoanion, [B3O3(OH)4]-, three contain the tetraborate dianion [B4O5(OH)4]2-, twelve contain the pentaborate anion, [B5O6(OH)4]-, three contain the hexaborate dianion, [B6O7(OH)6]2- and five contain heptaborate anions (three of which are [B7O9(OH)5]2-, and two are [B7O9(OH)6]3-). Additionally, two compounds contain two isolated polyborate anion species (octaborate dianion [B8O10(OH)6]2- with pentaborate anion [B5O6(OH)4]-, and triborate anion [B3O3(OH)4]- with [B5O6(OH)4]-). The crystal structures of fifteen salts containing these polyborate anions are reported: [Co(en)3][B5O6(OH)4][B8O10(OH)6]∙5H2O (6), [Co(NH3)6]2[B4O5(OH)4]3∙11H2O (9), s-fac-[Co(dien)2][B7O9(OH)6]∙9H2O (11), [Co(diNOsar)]2[B3O3(OH)4]Cl5∙4.75H2O (12), [Cu(en)2][B5O6(OH)4]2∙2H2O (20), [Cu(pn)2{B5O6(OH)4}][B5O6(OH)4]∙4H2O (22), [Cu(TMEDA){B6O7(OH)6}]∙6H2O (23), [Cu(dac)2(H2O)2][Cu(dac)2][B7O9(OH)5]2∙4H2O (24), [Cu(N,N-dmen)2(H2O)][B5O6(OH)4]2·3H2O (27), [Cu(N,N-dmen){B6O7(OH)6}]·4H2O (28), [Ni(en){B6O7(OH)6}(H2O)2]∙H2O (37), [Ni(AEN)][B5O6(OH)4]∙H2O (38), [Ni(dac)2(H2O-)2][Ni(dac)2][B7O9(OH)5]2∙4H2O (39), [Ni(hn)2][B5O6(OH)4]2 (40), and s-fac-[Ni(dien)2][B5O6(OH)4]2 (41). All the synthesized compounds reported were characterized using spectroscopic (IR, multi-element NMR) and analytical (melting point, elemental analysis, magnetic susceptibility, thermal analysis, powder X-ray diffraction) techniques. The solid-state structures of transition metal complex polyborate salts all display multiple cation-anion H-bond interactions and these undoubtedly play a major role in the energetics of engineering these structures. For example, in compound [Co(NH3)6]2[B4O5(OH)4]3∙11H2O (9), fourteen of the 18 amino hydrogen atoms of the [Co(NH3)6]3+ cation are involved in secondary coordination to anions via H-bonds. Two unique polyborate anions, [B8O10(OH)6)]2- and [B7O9(OH)6]3- have been prepared and characterized in [Co(en)3][B5O6(OH)4][B8O10(OH)6]∙5H2O (6) and s-fac-[Co(dien)2][B7O9(OH)6]∙9H2O (11), respectively. vii The reaction of transition metal complex cations with boric acid in different ratios produced polyborate compounds with different polyborate anions e.g. reaction of [Cu(en)2]2+ with boric acid in 1:10 and 1:5 ratios produce polyborate compounds with pentaborate(1-) and tetraborate(2-) anions, respectively. New polyborate anion structural architectures are identified in this thesis: (i) the pentaborate(1-) anion in [Cu(pn)2{B5O6(OH)4}][B5O6(OH)4]∙4H2O (22) acts as a monodentate ligand coordinated to the Cu(II) cation, (ii) the hexaborate(2-) anion in [Cu(TMEDA){B6O7(OH)6}]∙6H2O (23) and [Cu(N,N-dmen){B6O7(OH)6}]·4H2O (28) coordinates as a tridentate ligand with the Cu(II) cations, and (iii) the hexaborate(2-) anion in [Ni(en){B6O7(OH)6}(H2O)2]∙H2O (37) coordinates as a bidentate ligand with the Ni(II) cation. This is the first time that such coordination mode (i) and (iii) have been observed.

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Thuery, Pierre. "Transitions de spin dans la chimie moléculaire du cobalt(ii) et du fer (ii)." Paris 11, 1987. http://www.theses.fr/1987PA112341.

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Ce travail est principalement consacré à l'étude des transitions de spin dans des complexes du cobalt (II). Les synthèses d'une série de complexes penta- et hexacoordinés, ayant pour ligands équatoriaux des bases de Schiff et différents types de ligands équatoriaux des bases de Schiff et différents types de ligands axiaux, sont décrites. Les évolutions des susceptibilités magnétiques et des spectres RPE en fonction de la température permettent d'étudier l'influence de l'environnement de l'ion métallique sur son état de spin. Les propriétés observées sont interprétées sur la base de modèles simples. Plusieurs transitions de spin s - 1/2 - s = 3/2 thermo-induites sont mises en évidence. Par ailleurs, une corrélation peut être établie entre la géométrie et l'état de spin de ces complexes et leur aptitude à activer l'oxygène moléculaire. En vue de préciser le mécanisme de la transition de spin, des techniques d'investigations structurale et thermodynamique sont utilisées : la structure cristallographique de l'un des complexes est décrite, les variations moyennes des distances métal-ligand au cours de la transition sont évaluées par spectrométrie d'absorption des rayons X ; les variations d'enthalpie et de chaleur spécifique mesurées par ose sont confrontées aux valeurs calculées a partir d'un modèle phénoménologique. Enfin, une nouvelle façon de détecter la transition, grâce à son effet sur le spectre RPE d’un ion dopant Cu(II), est décrite dans le cas d'un complexe du fer(II) This work mainly deals with the spin crossover phenomenon in cobalt (II) molecular chemistry. The synthesis of a series of five- and six coordinated complexes, with Schiff bases as equatorial ligands and various apical ones, are reported. The temperature dependances of magnetic susceptibilities and EPR spectra are used to study the influence of the environment on the metal ion spin state. The behaviours observed are interpreted on the basis of simple models. Evidence is provided for thermally induced s = 1/2 - s -= 3/2 spin crossovers. In other respects, a correlation can be established between the geometry and spin state of these complexes and their ability to activate molecular oxygen. In order to specify the spin-crossover mechanism, structural and thermodynamic techniques are used: the ingle-crystal X-ray structure of one of the compounds is reported ; the mean variation of metal-ligand distances upon transition is evaluated by X-ray absorption spectroscopy; enthalpy and heat capacity changes, measured by DSC, are compared with the values calculated on the basis of a phenomenological model. A new means of detecting the crossover, by using its effect on the EPR spectrum of a Cu(II)doping ion, is described in the case of an iron (II) complex

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Castaldelli, Evandro. "Polímeros de coordenação à base de cobalto(II) e N,N'-bis(4-piridil)-1,4,5,8-naftaleno diimida como ligante e suas propriedade estruturais, espectroscópicas e fotoelétricas." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-25042016-110820/.

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Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características. Coordination polymers have been a major topic in materials science during the past decade, thanks to their versatility and virtually infinite possible combinations between metal centers and organic ligands. These coordination polymers usually inherit the properties of their components, such as magnetic, spectroscopic and electronic characteristics. However, despite the increasing number of research papers in this topic, it is still hard to find coordination polymers featuring electronic conductivity. To achieve that, we used a naphthalene diimide derivative, N,N\'-bis(4-pyridyl)-1,4,5,8- naphthalene diimide or NDI-py, which belongs to a class of rigid, planar, thermally and chemically stable compounds, extensively studied due to their photoelectrochemical properties and their n-type semiconductivity. The first coordination polymer synthesised, MOF-CoNDI-py-1, was an amorphous linear polymer, with a 1D structure. Based on these observations, MOF-CoNDI-py-2 was synthesised by using terephthalic acid as a supporting ligand, and it is a crystalline solid which its monoclinic unit cell belongs to a C2/c space group, as determined by single crystal X-ray diffraction. This network features a trinuclear high-spin Co(II) unit, and each metal ion sits on a distorted octahedra coordination geometry, while the NDI-py ligands sit in a parallel arrangement, with distances suitable for electronic transfers. A detailed study of their vibrational and electronic spectra, supported by DFT calculations, was performed, as well as a full description and assignment of the observed bands. MOF-CoNDI-py-2 absorbs in the whole studied spectral region, from 200 nm to 2500 nm, while it also features a ligand-centered emission spectrum. Electronic devices built around its crystals revealed electric conductivities of 7.9 10 -3 S cm -1, which is, to the best of our knowledge, the highest for a MOF to this date. This conductivity is also highly anisotropic, being significantly less conductive in certain directions. The current versus voltage profiles were analysed in terms of known conduction mechanisms, with best fits when using an electrode-limited Space-Charge Limited Current mechanism, in agreement with the proposition that this conductivity happens through the NDI-py stacking planes. Additionally, this mechanism is influenced by an external light source, being a photoconductor with a red laser, 632 nm, and a photoresistor with a white light. Combined, these results bring a light-modulated, highly conductive MOF material with an unusual structure. As far as we know, there are no similar MOFs in the literature, which makes MOF-CoNDI-py-2 one of a kind.

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Ortiz, Guillaume. "Synthèse de polymères de coordination poreux pour l'adsorption sélective du dioxyde de carbone." Thesis, Dijon, 2011. http://www.theses.fr/2011DIJOS018.

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La conception de matériaux capables de piéger sélectivement le CO2 revêt un enjeu majeur dans le développement de procédé de capture post-combustion pour de nombreux secteurs industriels. Nos travaux visent l'élaboration de nouveaux polymères de coordination de type MOF (“Metal-Organic Framework”) préparés par auto-assemblage de briques moléculaires polycarboxyliques avec des métaux de transition qui constituent les noeuds du réseau tridimensionnel. Ces matériaux hybrides microporeux présentent des propriétés d’adsorption du CO2 importantes. Notre approche a consisté à synthétiser des polymères de coordination dans le but d'accroître la capacité et la sélectivité d'adsorption du CO2 vis-à-vis d'autres gaz comme CO, CH4, N2 et O2 grâce à des interactions physiques impliquant le moment quadripolaire élevé du CO2 et le potentiel électrostatique existant dans les pores du matériau. Dans ce mémoire sont décrites les synthèses des différentes briques moléculaires organiques constituées de polyamines et de polyazamacrocycles Nfonctionnalisées par des terminaisons benzocarboxylate. Des matériaux homo- et hétéro- bimétalliques présentant des structures cristallines originales ont été obtenus à partir de briques moléculaires triazamacrocycliques N-fonctionnalisées par des terminaisons acides carboxyliques et différents cations métalliques (Zn2+, Co2+, Cd2+ et Ni2+). Les études de ces polymères de coordination poreux ont révélé leur capacité d’adsorption importante du CO2 avec une sélectivité remarquable dans les conditions normales de température et de pression The design of material able for CO2 capture is a major issue to achieve post-combustion capture process for many industries. Our work aims to develop new coordination polymer MOF (“Metal-Organic Framework”) prepared by self-assembling polycarboxylic linkers and transition metals. These microporous hybrids materials show important CO2 adsorption properties and are promising in the field of gas separation. The main topic of our work is to synthesise MOFs with high adsorption capacity and selectivity for CO2 over other gases (CO, CH4, N2 and O2). The gas-solid interactions are due to physical phenomena involving the high quadrupolar moment of CO2 and the electrostatic potential lying in the pore of the material. In this manuscript, the synthesis of various organic linkers incorporating N-functionalised polyamines and polyazamacrocycles with benzocarboxylate functions is described. Homo- and hetero- bimetallic materials with original tridimensional structure were obtained from a N-functionalised triazamacrocyclic linker and different metal cations (Zn2+, Co2+, Cd2+ and Ni2+). Studies of porous coordination polymers have shown high CO2 adsorption capacity with a remarkable selectivity in the ambient temperature and pressure conditions

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Farran, Rajaa. "Transfert d'électron photoinduit au sein d'assemblages hétérométalliques associant le [Ru(bpy)3]2+ à des complexes bisterpyridine du Fe(II), Co(III) et Cr(III)." Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAS009/document.

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La thèse commence le 1er octobre 2012. IL s'agit pour cette première année de thèse de synthétiser différents complexes de coordination a base du Ruthénium, Fer, Manganèse et de Cobalt à ligands polypyridinique. Ces complexes seront ensuite assemblés par lien covalent. Nous proposons d'utiliser entre autre les techniques d'electrochimie pour induire ces couplages. On cherchera aussi a immobiliser les assemblages sur surface. La principale difficulté attendue dans cette etape du travail concerne la fonctionalisation dissymétrique des ligands pour l'obtention de triade This thesis deals with the synthesis and characterization of inorganic triads for photoinduced charge separation. A range of photosensitizers will be studied, and the effect of the donor and acceptor will be assesed as well. These systems will be studied in solution and immobalized on surfaces. Cette thèse traite de la synthèse et la caractérisation des triades inorganiques pour la séparation de charge photoinduite. Une gamme de photosensibilisateurs seront étudiées, et l'effet du donneur et accepteur sera ainsi étudié. Ces systèmes seront étudiés en solution et immobalizes sur les surfaces

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Bulicanu, Vladimir. "Synthesis and study of magnetic molecular materials based on Co(II) and Cr(II) trinuclear clusters containing M-M bonds." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0239.

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Dans cette thèse est décrite la synthèse et les propriétés magnétiques des composés de coordination contenant des liaisons Co-Co ou Cr-Cr. Le contexte général sera discuté dans la première partie de ce travail en considérant l'évolution historique de ce type de chimie de coordination. Dans le deuxième chapitre, la possibilité d'intégrer un cluster {Co3} avec des ligands dipyridylamide et liaisons intermétalliques, dans des polymères de coordination unidimensionnels est discutée. Les interactions entre les porteurs de spin et l'effet du ligand pontant sont étudiés. Les changements des propriétés de transition de spin sont contrôlés en comparant par rapport au précurseur. Dans le troisième chapitre, les propriétés de molécule aimant d'un cluster de {Cr3} analogue à celui du {Co3}, sont étudiées. L'influence du ligand axial et la symétrie de la molécule sont également considérés et corrélées avec les propriétés de la molécule. Dans le quatrième chapitre, l'effet de la transition de spin induite par la coordination est étudié sur un exemple de cluster de {Co3} avec des ligands dipyridylformamidinate. La rupture et le rétablissement d'une liaison Co-Co est contrôlée par le biais de la température et de la lumière. L'effet de la rupture de la liaison intermétallique sur les propriétés magnétiques et structurales est aussi étudié In this thesis is described the synthesis, structures and magnetic properties of coordination compounds containing Co-Co or Cr-Cr bonds. In the first part of this work a general background is given on the historical evolution of this type of coordination chemistry. In the second chapter the possibility of incorporating a {Co3} cluster with dipyridylamide ligands and intermetallic bonds into one-dimentional coordination polymers is discussed. The interactions between spin centers and the effect of the bridging ligand were studied, and changes in the spin crossover properties were monitored and compared to the precursor. In the third chapter the Single-Molecule Magnet properties of a series of {Cr3} clusters are presented. The influence of the axial ligand and the symmetry of the molecule was considered and correlated to the magnetic properties. In the fourth chapter the phenomenon of coordination induced spin transition in a {Co3} cluster with dipyridylformamidinate ligands is discussed. Changes in magnetism and optical properties as a result of the breaking and restoring of a Co-Co bond were monitored as a function of temperature and light irradiation

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Coetzee, Jacorien. "New developments in the coordination chemistry of Gold(I), Gold(II) and Gold(III) with C-, N- , P-and S-donor ligands." Thesis, Stellenbosch : University of Stellenbosch, 2007. http://hdl.handle.net/10019.1/1702.

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Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. A comprehensive, comparative structural study of gold(I), gold(II) and gold(III) compounds with the general formula [Aux(C6F5)y(tht)z] (tht = tetrahydrothiophene) was performed. The series of compounds included the unprecedented dinucleur gold(II) compound, tetrakis(pentafluorophenyl)bis(tetrahydrothiophene)digold(II), which could be prepared in a rational manner. This very unique compound represents the first example of an unbridged dinucleur gold(II) compound in which the gold(II) centres are not stabilised by chelating ligands. Formation of this compound was postulated to have taken place by radical pentafluorophenyl (pfp) ligand migration along with AuII–AuII bond formation. It may therefore be regarded as a rare example of labile behaviour by a generally inert pfp ligand. In addition to this compound, the crystal and molecular structures of the wellknown gold(I) and gold(III) precursor compounds, (pentafluorophenyl)(tetrahydrothiophene) gold(I) and tris(pentafluorophenyl)(tetrahydrothiophene)gold(III) were carried out and are described for the first time. The latter underwent a unique mononuclear ligand rearrangement (metathesis or disproportionation) reaction in solution to yield the novel rearrangement product, bis(pentafluorophenyl)bis(tetrahydrothiophene)gold(III)tetrakis- (pentafluorophenyl)gold(III). In all the complexes, the Au–C and Au–S bond lengths displayed a variation which appears to be dependent on the oxidation state of the central gold atom. Both of these bond types were found to descrease in the order Au(II) > Au(III) > Au(I)...

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Lapprand, Antony. "Conception et propriétés photophysiques de polymères de coordination et de polymères organométalliques." Thesis, Besançon, 2015. http://www.theses.fr/2015BESA2031/document.

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Ces travaux portent sur la conception et l’étude des propriétés photophysiques de polymères de coordination et organométalliques. Dans un premier temps, nous nous sommes intéressés aux adduits formés à partir d’halogénure de cuivre(I) (CuxXyLz ; X= I, Br, Cl). Cette famille de composés possède une grande richesse structurelle de part les conditions de synthèse (choix du ligand, stoechiométrie, choix du solvant, température…) et des propriétés de luminescence variées. Nous nous sommes concentrés sur la synthèse, la caractérisation physique et photophysique d’adduits de CuX à ligands de types monothioéther (RSR) et dithioéther (RS(CH2)nSR). Nous avons ensuite étendu notre étude aux adduits CuX coordinés à des ligands P-chirogéniques (i.e chiralité portée par l’atome de phosphore) puis à des adduits CuX coordinés à la fois par des ligands phosphorés (PPh3 ou dppm) et par des ligands mono- ou dithioéthers. Dans un second temps, nous avons voulu connaître l’impact de l’incorporation de ligands P-chirogéniques (P(C17H35)(Ph)(i-Pr)) sur les propriétés photophysiques de polymères organométalliques conjugués 1D à base de platine(II) et de ligands arylbiséthynyles (-C≡C(Ar)C≡C-). Ce type de polymère basé sur le platine(II) est souvent utilisé comme modèle dans la compréhension des transferts d’énergie dans les états excités. Ces polymères, une fois caractérisés, ont été comparés aux analogues achiraux contenant le fragment trans-Pt(P(PBu)3)2 et plusieurs différences ont été notées. Les observations et conclusions sur la relation structure-propriété sont utiles pour la conception future de matériaux photoniques portant des groupements chiraux This work focuses on the design and study of photophysical properties of coordination and organometallics polymers. Initially, we focused on adducts formed from copper(I) halides (CuxXyLz; X = I, Br, Cl). Indeed, these compounds have great structural diversity depending on the synthesis conditions (nature of ligand, stoichiometry, choice of solvent, temperature...) and various luminescence properties. We focused on the synthesis, physical and photophysical characterization of copper(I) halide adducts based on monothioether (RSR) and dithioether (RS(CH2)nSR) ligands. Then, we extended our study to the adducts of copper(I) halide coordinated by phosphorus P-chirogenics ligands (ie chirality carried by the phosphorus atom) and then to CuX adducts coordinated by both phosphorus ligands (PPh3 or dppm)) and mono- or dithioether ligands. Secondly, the impact of the incorporation of P-chirogenics ligands (P(C17H35)(Ph)(i-Pr)) on the photophysical properties of organometallic conjugated polymers 1D based on platinum(II) and arylbisethynyles ligands (-C≡C(Ar)C≡C-) was investigated. This type of polymer based on platinum(II) is often used as a model for the understanding of excited states energy transfers. These polymers, once characterized, were compared to the achiral analogues containing the fragment of trans-Pt(P(PBu)3)2 and several differences were noted. The findings and conclusions on the structure-property relationship are useful in the future design of photonic materials bearing chiral groups

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Jouaiti, Abdelaziz. "Activation electrochimique de petites molecules par des composes bi-metalliques et elaboration de films polymeres conducteurs." Université Louis Pasteur (Strasbourg) (1971-2008), 1989. http://www.theses.fr/1989STR13036.

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Reduction electrocatalytique de co::(2) dans le dmf en presence de ni(cyclam)**(2+) (bis cyclam)**(4+). Modification d'electrodes par polymerisation electrolytique de differents complexes de fe ii, co ii et ru ii avec le coordinat (p-pyrrolylmethylphenyl)-4' terpyridine-2,2:6',2". Ce nouveau type d'electrodes peut jouer le role de mediateur redox

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Zakhia, Georges. "Synthèse, caractérisation et propriétés magnétiques de nano-aimants moléculaires." Thesis, Paris 11, 2015. http://www.theses.fr/2015PA112071.

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Dans la première partie de ce travail de thèse, nous nous sommes intéressé à l’étude de l’anisotropie magnétique au sein de complexes mononucléaires de Ni(II) et de Co(II) pentacoordinés de géométrie allant de la pyramide à base carrée jusqu’à la bipyramide trigonale. Pour les complexes mononucléaires, nous avons montré que pour une géométrie donnée, la nature de l’ion métallique a une influence importante sur l’anisotropie magnétique.Nous avons étudié l’effet de la géométrie pour un même ion métallique. Dans le cas d’une géométrie bipyramidale trigonale (symétrie C3v), nous avons montré que le complexe de Co(II) possède un axe facile de l’aimantation et donc un blocage de l’aimantation qui conduisent à l’ouverture d’un cycle d’hystérèse à basse température. Ce type de complexe peut donc être utilisé pour le stockage de l’information. Dans la deuxième partie du travail, nous avons étudié les propriétés magnétiques de complexes binucléaires. Un complexe binucléaire de Co(II) pontés par deux Cl- présente un faible couplage ferromagnétique et un blocage de l’aimantation.Enfin, l’autre aspect de ce travail est de réaliser une molécule binucléaire où deux ions anisotropes, chacun possédant un axe facile de l’aimantation, soient faiblement couplés de manière antiferromagnétique. Pour ce faire, nous avons étudié des composés avec des ligands de type cryptant où la géométrie autour des Co(II) est bipyramide trigonale. Nous avons trouvé qu’avec un ligand pontant de type Cl- ou Br-, l’interaction d’échange est beaucoup plus importante que l’anisotropie locale des ions Co(II) conduisant à un comportement magnétique où les ions perdent leur caractère local. Ce travail ouvre la perspective de synthétiser le même type de complexes mais avec des ponts de plus grande taille pour diminuer l’intensité du couplage antiferromagnétique In the first part of this thesis, we studied the magnetic anisotropy of pentacoordinated mononuclear Ni(II) and Co(II) complexes possessing geometries from square pyramid to trigonal bipyramid. We have shown that, for a given geometry, the metal ion nature has an important influence on the magnetic anisotropy.Then, we studied for a given metal ion the effect of geometry on its magnetic anisotropy. In the case of a trigonal bipyramidal geometry (C3v symmetry), we showed that Co(II) has an Ising type anisotropy (easy axis of magnetization) and thus a blocking of magnetization that leads to an opening of a hysteresis cycle at low temperature. This type of complexes can be used for storing data albeit at low temperature.In the second part of the work, we studied the magnetic properties of binuclear complexes. A binuclear Co(II) complex bridged by two Cl- has a weak ferromagnetic coupling and a blocking of its magnetization.Finally, another aspect of this work was to design binuclear complexes, where two anisotropic ions having each one an easy axis of magnetization, are weakly antiferromagnetically coupled. To do this, we have studied compounds with cryptand ligands where the geometry around the Co (II) is trigonal bipyramid. We found that with a Cl- or Br- bridging ligand, the exchange interaction is much more important than the local anisotropy of Co(II) ions leading to a magnetic behavior where the ions lose their local character. This work opens up prospects for synthesizing the same type of complex but with larger bridges to decrease the intensity of the antiferromagnetic coupling

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Ashoka, Sahadevan Suchithra. "Anilate-based molecular building blocks for metal-organic frameworks and molecular conductors Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks Nanosheets of Two-Dimensional Neutral Coordination Polymers Based on Near-Infrared-Emitting Lanthanides and a Chlorocyananilate Ligand." Thesis, Angers, 2019. http://bu.univ-angers.fr/Contact.

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Ce travail porte sur la synthèse et la caractérisation de matériaux moléculaires fonctionnels basés sur la molécule anilate et présentant des propriétés de conductivité, de magnétisme et de luminescence. Les anilates sont des dérivés de la 2,5-dihydroxy-1,4-benzoquinone substitués en positions 3 et 6 par une variété d’éléments (H, F, Cl, Br, I, CN, etc). Parmi eux, le seul composé hétérosubstitué ClCNAn2- a été choisi pour préparer une nouvelle famille de polymères de coordination bidimensionnels (PC 2D) avec des métaux de transition ou des ions lanthanides : i) un PC à valence mixte FeIIFeIII, de formule [TAG][FeIIFeIII(ClCNAn)3], contient pour la première fois le cation triaminoguanidinium dans un réseau de coordination.ii) Des PC basés sur le ligand ClCNAn2- et des ions lanthanides émettant dans le proche infrarouge (YbIII, NdIII, ErIII). Ces composés ont été exfoliés en monocouches, et des études de photoluminescence ont été menées à la fois sur les cristaux et les monocouches. iii) Une famille de PC hétéroleptiques basés sur des ions lanthanides et sur deux types de ligands pontants, le ligand ClCNAn2- et des ligands de type carboxylates (DOBDC et F4-BDC). iv) Une famille de PC basés sur des ions DyIII ont été préparés afin d’étudier leur propriétés magnétiques. v) Finalement, la capacité des ligands anilates à se combiner à des conducteurs moléculaires basés sur le BEDT-TTF a été démontrée à travers la synthèse et l’électrocristallisation de semiconducteurs organiques et de conducteurs magnétiques hybrides avec l’anion [Fe(ClCNAn)3]3- This work reports on the design, synthesis and characterization of novel anilate-based functional molecular materials showing luminescent, magnetic and/or conducting properties. The family of anilate ligands comprises several derivatives obtained by introducing various substituents (H, F, Cl, Br, I, CN, etc.) at the 3 and 6 positions of the common 2,5-dihydroxy-1,4-benzoquinone framework. Among the anilate ligands, the only known heterosubstituted anilate with Cl/CN substituents at the 3,6 positions, ClCNAn2-, have been selected for preparing a novel family of 2D layered coordination polymers (2D CP) with both 3d metal ions and 4f lanthanide ions, through a general and straightforward synthetic strategy. i) Mixed-valence FeIIFeIII 2D CP, formulated as [TAG][FeIIFeIII(ClCNAn)3], containing, the tris(amino)-guanidinium (TAG) cation for the first time in such 2D networks has been synthesized and thoroughly characterized. ii) 2D CPs based on NIR-emitting lanthanides (YbIII, NdIII, ErIII) and the ClCNAn2- ligand, have been prepared and characterized. These layered compounds were exfoliated to nanosheets, by sonication-assisted solution synthesis. Time-resolved photoluminescence studies performed on both the bulk and nanosheets are also highlighted. iii) Novel family of heteroleptic 2D CPs based on NIR-emitting lanthanides and mixed ligands (ClCNAn2- and carboxylate ligands (DOBDC and F4-BDC)), were prepared and characterized. vi) Novel family of 2D CPs based on DyIII and ClCNAn2- were prepared in order to investigate their magnetic properties. v) Furthermore, the ability of anilate ligands to work as components of BEDT-TTF- based molecular conductors have been demonstrated through the synthesis, via electrocrystallization technique. vi) П-d hybrid multifunctional paramagnetic molecular conductors BEDT-TTF and [Fe(ClCNAn)3]3-) were also studied

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Etrillard, Céline. "Synthèse de nanoparticules à transition de spin et étude des propriétés, application en électronique moléculaire." Phd thesis, Université Sciences et Technologies - Bordeaux I, 2011. http://tel.archives-ouvertes.fr/tel-00681515.

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L'objet de cette étude est d'utiliser la technique des micelles inverses pour synthétiser des nanoparticules à transition de spin, de taille et de forme contrôlées afin d'en permettre l'utilisation en électronique moléculaire. Dans la première partie, nous avons déterminé les paramètres de synthèse influençant la taille et la forme des particules d'un complexe à transition de spin à fort potentiel d'application. Dans un deuxième temps, nous avons utilisé ces paramètres sur trois autres complexes afin de comprendre la relation entre les paramètres de la synthèse et la morphologie des particules. Les nanoparticules ainsi synthétisées constituent la base d'une discussion sur l'existence d'un lien entre la taille/forme des particules et les propriétés de transition de spin. Enfin, la dernière partie de ce travail est consacrée à l'utilisation de ces matériaux en électronique moléculaire, et l'observation des propriétés de photoconductivité et photovoltaïque à l'échelle des nanoparticules.

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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.

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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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Chuang, PO-Hsiang, and 莊博翔. "Self-assembly, Structures and Magnetic Properties of Cobalt (II) Coordination Polymer with 2,3-Dihydroxyquinoxaline Ligand." Thesis, 2010. http://ndltd.ncl.edu.tw/handle/20541871091434600085.

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碩士 國立臺灣科技大學 工程技術研究所 98 In this thesis, 2,3-dihydroxyquinoxaline (H2L) was chosen as a ligand to react with Co2+ metal ion under hydrothermal conditions to prepare metal – organic coordination magnetic materials. Six coordination complexes, [Co(HL)(OAc)]n (1), [Co4(L)2(O2CPh)2(OMe)2(MeOH)2]n (2), [Co(HL)2(O2CPh)] (3), [Co(L’)2(OH2)] (4), [Co3(Btz)2(D-cam)2]n (5), and [Co2(BzIm)4(D-cam)2]n (6) were successfully synthesized. In the first part of this thesis, four Co-based complexes, 1?{4 were synthesized by using 2,3-dihydroxyquinoxaline of various coordination modes. Complex 1 adopted a one-dimensional single-chain structure. Complex 2 represents a 2D layer structure. Complexes 3 and 4 were discrete molecules. In particular, the Co metal center in 3 is trivalent. Furthermore, the structures, thermal stability, and physical properties of complexes 1?{4 were discussed. In the second part of this thesis, two Co(II) based complexes 5?{6 were synthesized by 2,3-dihydroxyquinoxaline and chiral ligand D - camphoric acid under hydrothermal conditions. Interestingly, two different ligands benzotriazole (Bta) and benzimidazole (BzIm) were unexpectedly generated in situ reaction from hydrolysis of 2,3-dihydroxyquinoxaline (H2L). Bta and BzIm coordinate with cobalt to form 5 with 2D architecture and 6 with 1D architecture, respectively, and both of which have chiral space group. Furthermore, the structures, thermal stability, and physical properties of complexes 5?{6 were discussed. Moreover, we focused on the magnetic properties of complexes 1, 2, and 5. In complex 1, results from DC magnetic susceptibility measurement revealed that spin-canted antiferromagnetic interactions within the CoII ions. The susceptibility also showed weak ferromagnetic interaction at low temperature. In addition, the ZFC-FC magnetization and hysteresis loop data confirmed that 1 exhibits single chain magnet of antiferromagnetic spin-canting behavior at low temperature. Complex 2, its DC magnetic susceptibility, ZFC-FC magnetization were also studied. These data indicated the divergence phenomenon of 2 below 12 K. The hysteresis loop of magnetization vs field at 10 K could also be observed. According to the AC magnetic susceptibility and hysteresis loop, we further confirmed that spin-glass behavior of 2 from spin-canting magnetic interaction. In complex 5, results from DC magnetic susceptibility measurement revealed that antiferromagnetic interactions within the CoII ions.

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Kuo, Po-Ting, and 郭柏廷. "Synthesis, Structures and Properties of Cobalt(II) Coordination Polymer Containing Dipyridyl Amide and Camphorate Ligands." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/45643453964026438064.

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碩士 中原大學 化學研究所 100 This thesis discusses the synthesis and structures of six new metal – organic frameworks containing D,L – camphorate(D,L-camph) and dipyridyl amide ligands. The solventhermal reactions of these ligands with Co(II) salts afforded six complexes of [Co2(D-camph)2(L1)]•2H2O (1), [Co2(D-camph)2 (L2)] •2H2O (2), [Co2(L-camph)2(L2)]•2H2O (3), [Co2(D,L-camph)2(L2)]•2H2O (4), Co2(D-camph)2(L3) (5) and Co(D-camph)(L4) (6). All the complexes have been characterized by EA, IR, UV-vis, TGA, power X-ray diffraction and single crystal X-ray diffraction. Complex 1 shows the (486108) roa topology, which involves four six-membered rings ( 1 + 3 ) with 3D self-penetrating net. Although L3 is longer then L2, complexes 2 - 5 have the same (41263) pcu topology. The chiral layer formed by camphorate ligand are important in determining the structural type. Complex 6 shows the 2D → 2D 3-fold interpenetration, with the (4)(4•85) topology for the net.

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He, Hsiu-Yi, and 何修億. "Synthesis, Structures and Properties of Cadmium (II) and Cobalt(II) Coordination Polymers with Dipyridyl Amide and Polycarboxylate Ligands." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/8y3uf2.

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碩士 中原大學 化學研究所 102 This thesis discusses the synthese, structures and properties of nine new coordination polymers containing dipyridyl amide and polycarboxylate ligands, including {[Cd(1,2-BDC)(L1)(H2O)]•H2O}n [L1 = N,N¢-di(3-pyridyl)suberoamide; 1,2-H2BDC = benzene-1,2-dicarboxylic Acid], 1; {[Cd2(1,3-BDC)2(L1)3]•8H2O}n (1,3-H2BDC = benzene-1,3-dicarboxylic Acid), 2; {[Cd0.5(1,4-BDC)0.5(L1)0.5(H2O)]}n (1,4-H2BDC = benzene-1,4-dicarboxylic Acid), 3; {[Cd(1,3-BDC)(L1)]•H2O}n, 4; [Cd(5-OH-IPA)(L1)]n (5-OH-IPA = 5-hydroxyisophthalic Acid), 5; {[Cd3(BTC)2(L1)3(H2O)3]•8H2O}n (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic Acid), 6; [Co(5-OH-IPA)(L1)]n, 7; [Cd(5-Br-IPA)(L2)]n [L2 = N,N¢-di(4-pyridyl)suberoamide; 5-Br-H2IPA = 5-bromoisophthalic Acid], 8; [Cd(5-tert-IPA)(L2)0.5]n (5-tert-H2IPA = 5-tert-butylisophthalic Acid), 9. All the complexes have been characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, thermogravimetric analyses, infrared spectrometer and fluorescence spectrometer. Complex 1 forms a loop-like 1D chain. Complex 2 forms a 3D framework with a new (65.8) topology. Complex 3 forms a 2D layer with a sql topology. Complexes 4, 5, and 7 show 2D double layers with a 3,5L2 topology. Complex 6 forms a 3D framework with a 3,4,4T90 topology. Complex 8 forms a two-fold interpenetrated 2D layer with a 2,6L1 topology. Complex 9 forms a 3D framework with a {510.63.7.8}{54.62} topology.

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Wu, Tsung-Tai, and 吳宗泰. "Synthesis, Structures and Properties of Cobalt(II) and Nickel(II) Coordination Polymers Containing Dipyridyl Amide and V-shaped Dicarboxylate Ligands." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/xbnk75.

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碩士 中原大學 化學研究所 102 A series of Co(II) and Ni(II) coordination polymers containing N,N-di(4-pyridyl)suberoamide (L) and V-shaped dicarboxylate ligands: {[Co(L)(MBA)]2H2O}n (L = N,N’-di(4-pyridyl)suberoamide; H2MBA = diphenylmethane-4,4’–dicarboxylic acid), 1, {[Ni(L)(MBA)]2H2O}n, 2, {[Co2(L)(MBA)2]2CH3OH}n , 3, {[Co2(L)(MBA)2]}n, 4, {[Co2(L)(OBA)2]7CH3OH}n [H2OBA = 4,4’–oxybis(benzoic acid)], 5, {[Co(L)(H2hfipbb)]2H2O}n [H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)], 6, {[Co(L)(SDA)]H2O}n (H2SDA = 4,4’-sulfonyldibenzoic acid), 7, {[Ni(L)(SDA)]2H2O}n, 8, are reported, which were prepared by hydrothermal reactions. Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, powder X-ray diffraction and thermal gravimetric analysis. The CO2 capture is preferable to N2 and H2 in the gas sorption for the desolvated product of 5. Complex 1 and 2 are 1D → 2D polycatenanes derived from the helical channels. Complex 3 shows the (42688104)(4)2-2,6L1 topology with a 2-fold interpenetrating mode. Complex 4 shows 2D layers with the (42688104)(4)2 2,6L1 topology, which catenate to each other to form a 2D → 3D inclined polycatenation framework. Complex 5 shows (63)(698)-gra topology with a 3-fold interpenetrating mode. The unusual topological features of 6 - 8 consists of the 2- and 3-fold interpenetrated layers with the (64810)(6) topology, which are further catenated to the two adjacent such sheets in parallel fashion to give overall unique 2D → 3D polycatenated frameworks.

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Ding, Miao-Tzu, and 丁妙慈. "Soluble Metal-Organic Frameworks: Dissolution/Reassembly towards the Structural Rearrangement of Porous Cobalt(II)- and Nickel(II)–Carboxylate Coordination Polymers." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/40897218316524320914.

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碩士 國立中央大學 化學研究所 96 The goal of this study was to develop a self-assembly synthetic strategy for the preparation of metal–organic coordination polymers using benzene-1,2,4,5-tetracarboxylic acid (H4btec) and transition-metal ions (CoII, NiII). Four three-dimensional, soluble, porous metal–organic coordination networks {K2[Co3(btec)2(H2O)4]∙6H2O}n (1•6H2O), {K2[Ni3(btec)2(H2O)4]•4H2O}n (2•4H2O), {Cs2[Co3(btec)2(H2O)4]•3H2O}n (3•3H2O), and {Cs2[Ni3(btec)2(H2O)4]•3H2O}n (4•3H2O) with near identical structural features were hydrothermally prepared. These structures adopt a (4,8)-connected net consisting of a four-connected square-planar node of a btec4－ ligand and an eight-connected node of trinuclear clusters M3(O2C)8(H2O)4. These three-dimensional frameworks possess hydrophilic channels, where the alkali metal ions (KI or CsI) and free water molecules reside. Ion-exchange studies, by treating 1～4 in an aqueous solution of alkali chloride (LiCl, NaCl, CsCl and KCl), revealed that a surprisingly dissolution/reassembly process occurred, leading to the rearrangement of metal–carboxylate building blocks and the formation of new metal–carboxylate species (5～13). The structural transformations were confirmed by single-crystal and powder X-ray diffraction (PXRD) data

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"Characterization of cobalt porphyrin coordination polymer: Ab initio structure by DFT method." 2002. http://library.cuhk.edu.hk/record=b5891144.

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Fong Ching-yee. Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. Includes bibliographical references (leaves 72-76). Abstracts in English and Chinese. ABSTRACT (English Version) --- p.iii ABSTRACT (Chinese Version) --- p.v ACKNOWLEGEMENT --- p.vi TABLE OF CONTENTS --- p.vii LIST OF TABLES --- p.ix LIST OF FIGURES --- p.xi LIST OF APPENDICES --- p.xiii Chapter CHAPTER ONE --- Introduction Chapter 1.1 --- Importance and Recent Development in Metalloporphyrin --- p.1 Chapter 1.2 --- Structure of Metalloporphyrin --- p.2 Chapter 1.3 --- General Properties of Metalloporphyrin --- p.4 Chapter 1.4 --- Linkage Patterns of Metalloporphyrin Polymers --- p.7 Chapter 1.5 --- Reasons for Studying Co-Por-Au Polymer --- p.10 Chapter CHAPTER TWO --- Cobalt Porphyrin Gold (Co-Por-Au) Polymer Model Chapter 2.1 --- Synthetic Scheme --- p.13 Chapter 2.2 --- Experimental Results and Related Properties --- p.14 Chapter 2.3 --- The Structure of Co-Por-Au Polymer --- p.18 Chapter CHAPTER THREE --- Structure Characterization of Co-Por-Au Polymer by DFT Method Chapter 3.1 --- Quantum Chemical Calculations --- p.21 Chapter 3.2 --- Density Functional Theory --- p.22 Chapter 3.3 --- Computational Details --- p.24 Chapter 3.4 --- Justification for using Gaussian 98 and VASP --- p.27 Chapter 3.5 --- Results and Discussions --- p.30 Chapter 3.5.1 --- Monomers of TPHP and TPCNP --- p.30 Chapter 3.5.1.1 --- The Geometry of the Monomer Structures of TPhP and TPCNP --- p.30 Chapter 3.5.1.2 --- The Axial Coordination Mode of Monomer in TPhP and TPCNP --- p.34 Chapter 3.5.1.3 --- Comparison between Hybrid DFT and Pure DFT method --- p.38 Chapter 3.5.1.4 --- Comparison with Other Porphyrin System --- p.40 Chapter 3.5.1.5 --- Summary --- p.43 Chapter 3.5.2 --- Polymers of TPhP and TPcnP --- p.44 Chapter 3.5.2.1 --- (μ-pyrazine)(octaethylporphyrinato)iron(II) {[Fe(OEP)pyz]}n --- p.44 Chapter 3.5.2.2 --- Energetic Comparison of TPHP and TPCNP with Different Axial Coordination Modes --- p.46 Chapter 3.5.2.3 --- Geometry of the Repeating Units in the Polymer of TPhP and TPCNP --- p.48 Chapter 3.5.2.4 --- Comparison with Other Porphyrin System --- p.52 Chapter 3.5.2.5 --- The Electronic Structures of TPHP and TPCNP --- p.55 Chapter 3.5.2.6 --- Summary --- p.58 Chapter CHAPTER FOUR --- Conclusion --- p.59 APPENDIX I-III --- p.61 REFERENCES --- p.72

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ZHANG, CHUN-SONG, and 張春松. "Bifuran derivatives, studies of synthesis and their coordination with cobalt (II) chloride and nickel (II) chloride." Thesis, 1988. http://ndltd.ncl.edu.tw/handle/55899663984305854740.

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Zhang, Chun-Song, and 張春松. "Bifuran derivatives, studies of synthesis and their coordination with cobalt (II) chloride and nickel (II) chloride." Thesis, 1988. http://ndltd.ncl.edu.tw/handle/94933362674016502764.

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Tong, Wai-Chi, and 湯偉治. "Coordination Polymer-derived Cobalt-embedded carbon fiber as an efficient heterogeneous catalyst for activating peroxymonosulfate." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/96j7zs.

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WANG, FANG-YU, and 王方宇. "Derivatives of thiophene、furane、pyrrol、pyridine, studies of synthesis and their coordination with cobalt (II) perchlorate." Thesis, 1989. http://ndltd.ncl.edu.tw/handle/31816823005608550623.

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Sie, Ming-Jhe, and 謝明哲. "Synthesis, Structures and Properties of Cadmium (II) Coordination Polymer with Dipyridyl Amide and Dicarboxylic Acid Ligands." Thesis, 2011. http://ndltd.ncl.edu.tw/handle/46145112642124136767.

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碩士 中原大學 化學研究所 99 This thesis discusses the synthesis and structures of three new metal - organic frameworks (MOFs) containing dipyridyl amide and dicarboxylate ligands. The Cd(II) complexes [Cd(bpdc)(L1)]n (1)．1.5DMF, {[Cd2(1,4-ndc)2(L1)2(H2O)]．H2O．2DMF}n (2) and {[Cd(1,4-ndc)(L2)(H2O)]．2H2O}n (3) have been prepared by the hydrothermal reactions of Cd(II) salts with N,N'-di(4-pyridyl)adipoamide (L1), N,N'-di(3-pyridyl)adipoamide (L2), 4,4'-biphenyldicarboxylic acid (H2bpdc) and naphthalene-1,4-dicarboxylic acid (1,4-H2ndc). All the complexes have characterized by single crystal X-ray diffractometer, powder X-ray diffractometer, elemental analyzer, thermogravimetric analyzer, infrared spectrophotometer, ultraviolet/visible spectrophotometer, gas absorption and fluorescence spectrophotometer. Single crystal X-ray diffraction showed that complex 1 forms a two-fold interpenetrated 3D framework with a (42,64)(43,67)2 topology, while complex 2 forms a three-fold interpenetrated 3D framework with a (4,62)(42,63,8)(43,65,82) topology and complex 3 displays a 2D → 3D polycatenated framework with a (44,62) topology. Although interpenetration occurs in complex 1, it still exists channels along c axis, with cross sections about 15.65 × 15.65 Å2 and the solvent-accessible volume is 47.8 % of the unit cell volume. However, due to the three-fold interpenetration in 2, the solvent-accessible volume of complex 2 is only 19.4 % of the unit cell volume. The solvent-accessible volume of complex 3 is 9.4 % of the unit cell volume.

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Almaraz, Elky. "The Interactions of Zinc Thiolate Complexes and Exogenous Metal Species: Investigations of Thiolate Bridging and Metal Exchange." 2009. http://hdl.handle.net/1969.1/ETD-TAMU-2009-05-536.

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Small molecule Zn(II) complexes containing N- and S- donor environments may serve as appropriate models for mimicking Zn protein sites, and thus, their reactions with heavy metal ions such as Pt(II) and W(0) may provide insight into possible adduct formation and zinc displacement. To study such possible interactions between zinc finger proteins and platinum-bound DNA, the ZnN2S2 dimeric complex, N,N?-bis(2- mercaptoethyl)-1,4-diazacycloheptane zinc (II), [Zn-1?]2, has been examined for Znbound thiolate reactivity in the presence of Pt(II) nitrogen ? rich compounds. The reactions yielded Zn/Pt di- and tri- nuclear thiolate-bridged adducts and metalexchanged products, which were initially observed via ESI-mass spectrometry (ESI-MS) analysis of reaction solutions, and ultimately verified by comparison to the ESI-MS analysis, 195Pt NMR spectroscopy, and X-ray crystallography of directly synthesized complexes. The isolation of Zn-(?-SR)-Pt-bridged [(Zn(bme-dach)Cl)(Pt(dien))]Cl adduct from these studies is, to our knowledge, the first Zn-Pt bimetallic thiolatebridged model demonstrating the interaction between Zn-bound thiolates and Pt(II). Additional derivatives involving Pd(II) and Au(III) have been explored to parallel the experiments executed with Pt(II). The [Zn-1?]2 was then modified by cleavage with Na+[ICH2CO2]- to produce (N- (3-Thiabutyl)-N?-(3-thiapentaneoate)-1,4-diazacycloheptane) zinc(II), Zn-1?-Ac or ZnN2SS?O, and 1,4-diazacycloheptane-1,4-diylbis(3-thiapentanoato) zinc(II), Zn-1?-Ac2 or ZnN2S?2O2, monomeric complexes (where S = thiolate, S? = thioether). The [Zn-1?]2 di- and Zn-1?-Ac mono-thiolato complexes demonstrated reactivity towards labile-ligand tungsten carbonyl species, (THF)W(CO)5 and (pip)2W(CO)4, to yield, respectively, the [(Zn-1?-Cl)W(CO)4]- complex and the [(Zn-1?-Ac)W(CO)5]x coordination polymer. With the aid of CO ligands for IR spectral monitoring, the products were isolated and characterized spectroscopically, as well as by X-ray diffraction and elemental analysis. To examine the potential for zinc complexes (or zinc-templated ligands) to possibly serve as a toxic metal remediation agents, Zn-1?-Ac and Zn-1?-Ac2 were reacted with Ni(BF4)2. The formation of Zn/Ni exchanged products confirmed the capability of ?free? Ni(II) to displace Zn(II) within the N-, S-, and O- chelate environment. The Zn/Ni exchanged complexes were analyzed by ESI-MS, UV-visible spectroscopy, IR spectroscopy of the acetate regions, and X-ray crystallography. They serve as foundation molecules for more noxious metal exchange / zinc displacement products.

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27

Leblanc, Mathieu. "Hydroxyamidinates et polymères de coordination : suspicions et valences mixtes." Thèse, 2015. http://hdl.handle.net/1866/15928.

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Dans un contexte où l’énergie représente un enjeu majeur pour les pays et organisations à économies émergentes et développées, la recherche de nouvelles sources renouvelables et la démocratisation des vecteurs énergétiques permettant l’approvisionnement mondial de façon durable constitue un devoir pour la communauté scientifique internationale. D’ailleurs, il serait essentiel que les nombreuses disciplines de la chimie concertent leurs efforts. Plus particulièrement, la croissance de la recherche en chimie de coordination orientée vers la photosynthèse artificielle ainsi que le développement de matériaux fonctionnels démontre l’importance indéniable de ce champ de recherche. Ce travail présente dans un premier temps l’étude des différentes voies de synthèse d’hydroxyamidines, un ligand chélatant aux propriétés de coordination prometteuses ne recevant que très peu d’attention de la part de la communauté scientifique. Dans un deuxième temps, nous présenterons le développement d’une stratégie d’assemblage de leurs complexes supramoléculaires impliquant des métaux de transition abondants et peu dispendieux de la première rangée. Dans un troisième temps, il sera question de l’investigation de leurs propriétés photophysiques et électrochimiques à des fins d’applications au sein de matériaux fonctionnels. Pour ce faire, les différentes voies de synthèse des hydroxyamidines et de leurs amidines correspondantes qui ont précédemment été étudiées par les membres du groupe seront tout d’abord perfectionnées, puis investiguées afin de déterminer leur versatilité. Ensuite, les propriétés de complexation des amox résultantes comportant des motifs sélectionnés seront déterminées pour enfin étudier les propriétés photophysiques et électrochimiques d’une série de complexes de métaux de transition de la première rangée. En somme, plusieurs designs qu’offrent les amox et bis-amox sont étudiés et les propriétés des architectures résultantes de leur auto-assemblage sont déterminées. In a context where energy supply represents a major challenge for countries and organizations with emerging and developed economies, the search for new renewable resources and the democratization of energy vectors allowing sustainable worldwide supply is a responsibility for the international scientific community. Besides, it would be essential that the many disciplines of chemistry concerted their efforts. In particular, the growth of research in coordination chemistry oriented toward artificial photosynthesis and the development of functional materials demonstrates the undeniable importance of this field of research. The first part of the work presents different synthetic routes to hydroxyamidines, a chelating ligand with promising properties and receiving very little attention from the scientific community. Secondly, we present the development of a strategy of assembly of their supramolecular complexes involving abundant and cheap first row transition metal. Thirdly, we will discuss the investigation of their photophysical and electrochemical properties for their purposes in functional materials applications. To do this, the different synthesis routes of hydroxyamidines and their corresponding amidines which have previously been studied by other members of the group will first be improved then investigated to determine their versatility. Next, the complexing properties of the resulting amox having selected patterns will be determined to finally study the photophysical and electrochemical properties of a series of first row transition metal complexes. In sum, the various designs offered by amox and the bis-amox complexes are studied and the properties of the resulting architectures of their self-assemblies are determined.

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