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Author: Nicola Michelle Cox Publisher: ISBN: Category : Languages : en Pages :
Book Description
This thesis describes three areas of research which involve preparation of novel pyridyl-thiazole-containing ligands and the formation of their complexes with transition metal ions. Chapter 2 describes the preparation, complexation chemistry and photophysical behaviour of ligands L1 and L2 which contain pyrene moieties. The emission properties of pyrene are highly dependent on its environment, and so it was proposed that it could be used as a probe to elucidate solution conformations of complexes. It was shown that incorporation of a pyrene moiety into the ligand strand and subsequent measurement of the emission spectra of its complexes with Cu+ and Cd2+ gave information about their solution state conformations which correlated well with the solid state structures. In Chapter 3, synthesis and coordination complexes of ligands L3 and L4, which contain substituents capable of binding anions, are described. L3 forms a mononuclear complex with Zn(II) which binds two perchlorate anions via the amide groups on the two substituents. However, with Cu(I), L3 and L4 form dinuclear double helicates which have a binding "pocket" at each end of the complex. Both [Cu2(L3)2](ClO4)2 and [Cu2(L4)2](PF6)2 form one-dimensional polymers; the complexes are held together by bridging perchlorate and hexafluorophosphate anions, respectively. Finally, in Chapter 4, allosteric control of the complexation behaviour of ligand L5 is described. L5 contains amine groups on the 3,3'-positions of the bipyridine core which can react with ketones, forming a cyclic aminal product. Reaction with cyclohexanone was used to control the metal specificity of the ligand by restraining the torsion angle between the two pyridine groups and forcing the ligand into planarity. In general, L5 formed dinuclear double helicates with tetrahedral metals and mononuclear complexes with octahedral metals, as expected. Upon reaction with cyclohexanone, mononuclear species were observed with Hg2+, Zn2+, Cd2+ and Ag+. Experiments were then carried out with mixtures of metal ions and two trends were observed: firstly, when L5 is mixed with octahedral and tetrahedral metals, species containing the octahedral metal are favoured. Where two octahedral metals are used species containing the metal with the larger ionic radius are formed preferentially. After reaction with cyclohexanone, only mononuclear species of the octahedral metals are observed in every case.
Author: Nicola Michelle Cox Publisher: ISBN: Category : Languages : en Pages :
Book Description
This thesis describes three areas of research which involve preparation of novel pyridyl-thiazole-containing ligands and the formation of their complexes with transition metal ions. Chapter 2 describes the preparation, complexation chemistry and photophysical behaviour of ligands L1 and L2 which contain pyrene moieties. The emission properties of pyrene are highly dependent on its environment, and so it was proposed that it could be used as a probe to elucidate solution conformations of complexes. It was shown that incorporation of a pyrene moiety into the ligand strand and subsequent measurement of the emission spectra of its complexes with Cu+ and Cd2+ gave information about their solution state conformations which correlated well with the solid state structures. In Chapter 3, synthesis and coordination complexes of ligands L3 and L4, which contain substituents capable of binding anions, are described. L3 forms a mononuclear complex with Zn(II) which binds two perchlorate anions via the amide groups on the two substituents. However, with Cu(I), L3 and L4 form dinuclear double helicates which have a binding "pocket" at each end of the complex. Both [Cu2(L3)2](ClO4)2 and [Cu2(L4)2](PF6)2 form one-dimensional polymers; the complexes are held together by bridging perchlorate and hexafluorophosphate anions, respectively. Finally, in Chapter 4, allosteric control of the complexation behaviour of ligand L5 is described. L5 contains amine groups on the 3,3'-positions of the bipyridine core which can react with ketones, forming a cyclic aminal product. Reaction with cyclohexanone was used to control the metal specificity of the ligand by restraining the torsion angle between the two pyridine groups and forcing the ligand into planarity. In general, L5 formed dinuclear double helicates with tetrahedral metals and mononuclear complexes with octahedral metals, as expected. Upon reaction with cyclohexanone, mononuclear species were observed with Hg2+, Zn2+, Cd2+ and Ag+. Experiments were then carried out with mixtures of metal ions and two trends were observed: firstly, when L5 is mixed with octahedral and tetrahedral metals, species containing the octahedral metal are favoured. Where two octahedral metals are used species containing the metal with the larger ionic radius are formed preferentially. After reaction with cyclohexanone, only mononuclear species of the octahedral metals are observed in every case.
Author: John Hardy Publisher: Royal Society of Chemistry ISBN: 1782620222 Category : Science Languages : en Pages : 416
Book Description
There is great interest in metallosupramolecular materials because of their use in magnetic, photonic and electronic materials. Functional Metallosupramolecular Materials focuses on the applications of these materials covering the chemistry underlying the synthesis of a variety of ligands to coordinate various metal ions and the generation of 2D and 3D materials based on these constructs. The book starts by looking at different metallosupramolecular systems including naturally occurring functional metallosupramolecular materials; DNA-based metallosupramolecular materials; metallopolymers; metallogels as well as functional materials based on MOFs. Subsequent chapters then systematically cover the different applications such as molecular computation, spin-crossover, light harvesting and as photocatalysts for the production of solar fuels. The book provides an overview of functional metallosupramolecular materials that will be of interest to graduate students, academics and industrial chemists interested in supramolecular chemistry, materials science and the materials applications. Priced at £159.00, US$260.00, €198.75
Author: John George Hardy Publisher: Royal Society of Chemistry ISBN: 1782622675 Category : Technology & Engineering Languages : en Pages : 417
Book Description
There is great interest in metallosupramolecular materials because of their use in magnetic, photonic and electronic materials. Functional Metallosupramolecular Materials focuses on the applications of these materials covering the chemistry underlying the synthesis of a variety of ligands to coordinate various metal ions and the generation of 2D and 3D materials based on these constructs. The book starts by looking at different metallosupramolecular systems including naturally occurring functional metallosupramolecular materials; DNA-based metallosupramolecular materials; metallopolymers; metallogels as well as functional materials based on MOFs. Subsequent chapters then systematically cover the different applications such as molecular computation, spin-crossover, light harvesting and as photocatalysts for the production of solar fuels. The book provides an overview of functional metallosupramolecular materials that will be of interest to graduate students, academics and industrial chemists interested in supramolecular chemistry, materials science and the materials applications.
Author: Publisher: ISBN: Category : Languages : en Pages :
Book Description
A series of para-dioxolene bridging ligands with bis-tridentate or bis-bidentate coordination pockets have been prepared. These ligands were designed to serve as building blocks in the preparation of functional metallosupramolecular structures. The bis-tridentate dipyridyl-diazaanthraquinones have topologies suitable for the preparation of [2 x 2] grids or larger extended structures. Employing a double condensation reaction between 1,3-diamino-4,6-benzenedicarboxaldehyde and 2-acetyl pyridine successfully afforded a cisoid binding diazaanthraquinone. The redox activity of the latter revealed it is more easily reduced than structurally similar 1,5- and 1,8-diazaanthraquinones. The synthesis of an analogous ligand displaying transoid coordination pockets proved challenging. Several approaches were attempted however the preparation of key intermediates 1,4-dinitro-2,5-benzenedicarboxaldehyde and 2,5-diamino-1,4-(hydroxyI-methyl) benzene were unsuccessful. A collection of bis-bidentate 2,5-bis(phosphino)1,4-dioxolenes were prepared with diphenyl, diisopropyl and diethoxy substituents at the phosphorus center. 2,5- Dibromo-1,4-dimethoxybenzene was reacted with the appropriate chlorophosphine under lithiation conditions to afford the dimethoxy compound, which was subsequently deprotected to the hydroquinone state with a Lewis acid. The diphenylphosphino hydroquinone was oxidized using phenyliodonium bisacetate, however efforts to oxidize other hydroquinone precursors to the targeted quinone state proved challenging. Diphenyl and diisopropyl phosphino hydroquinones were successfully coordinated with diamagnetic palladium hexafluoroacetylacetonate precursors. The resulting bimetallic bis(phosphino) dianion complexes were subsequently oxidized to the semiquinone state using silver (I) hexafluorophosphate and studied to determine the distinctive features of the semiquinone ligand.
Author: Dieter Wöhrle Publisher: Wiley-VCH ISBN: Category : Science Languages : en Pages : 700
Book Description
Metals and metal complexes can form compounds with organic macromolecules that show amazing properties. As is so often the case, nature leads by example. Synthetically produced model compounds, such as phthalocyanines, porphyrines or metalloproteins, as well as metallorganic polymers have aroused much interest in materials science. Their special magnetic, electrochemical and photochemical properties open up new perspectives in microelectronics and sensors. This compact manual is aimed at all organic, inorganic, polymer and physical chemists as well as materials scientists looking for competent and detailed information on the current state of this interdisciplinary area of research. It covers all questions relating to the targeted design of metallic macromolecules, from proven synthesis methods right up to the latest strategies. It also treats major progress in the determination of their structures, the physical-chemical properties of promising compounds and their potential in microelectronics and sensors. Furthermore, the most important methods of synthesis and investigation are presented in detail in an experimental section, while a comprehensive collection of pertinent original literature round s off this unique reference on all matters relating to macromolecular metal complexes.
Author: Sankarasekaran Shanmugaraju Publisher: Elsevier ISBN: 0323907059 Category : Science Languages : en Pages : 498
Book Description
Supramolecular Coordination Complexes: Design, Synthesis, and Applications discusses the growth of the field and explores the advantages, opportunities and latest applications of supramolecular complexes. Beginning with an introduction to design principles, synthetic methods, and post-synthetic functionalization of supramolecular complexes, the book goes on to compile the different analytical and computational modeling methods used to understand the structure and functional properties of supramolecular structures. Applications of supramolecular complexes in biomedicine, sensing, catalysis and materials are then explored in detail. Drawing on the knowledge of a global team of experts, this book provides a wealth of interesting information for students and researchers working in the design, synthesis or application of such complexes. Discusses cutting-edge approaches for the investigation of supramolecular coordination chemistry Summarizes a varied range of supramolecular coordination, complex designs and applications Highlights the interdisciplinary connections between supramolecular chemistry and the fields of biology and materials science
Author: Rahul Banerjee Publisher: Royal Society of Chemistry ISBN: 1782625402 Category : Science Languages : en Pages : 477
Book Description
This book provides a comprehensive review of the structure and function of organic and metal-organic supramolecular materials, which will be of interest to students and researchers in this field.
Author: Zaozao Qiu Publisher: Springer Science & Business Media ISBN: 3642243606 Category : Science Languages : en Pages : 143
Book Description
Zaozao Qiu shows in this thesis that transition metals can mediate or catalyze the cycloaddition or coupling reactions of carboryne with alkynes or alkenes to afford benzocarboranes, alkenylcarboranes or dihydrobenzocarboranes. These results represent powerful strategies to assemble useful complex molecules from very simple precursors in a single operation. Carboranes have many applications in medicine. However, their unique structures make derivatization difficult and the limited efficient synthetic methods to obtain functional carborane materials have restricted applications of carboranes within a narrow scope. This work breaks a new ground in metal-carboryne chemistry and will have a significant impact on synthetic, cluster and materials chemistry.
Author: Nicola Michelle Cox
Author: Nicola Michelle Cox
Author: John Hardy
Author: Hai-Bo Yang
Author: John George Hardy
Author: 
Author: Sharon Lindsay Caldwell
Author: Dieter Wöhrle
Author: Sankarasekaran Shanmugaraju
Author: Rahul Banerjee
Author: Zaozao Qiu