Synthesis of polydentate ligands and the formation of heterometallic and circular helicates PDF Download
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Author: Martina Whitehead
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Languages : en
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Author: Martina Whitehead
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Author: Martina Whitehead
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Languages : en
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Described herein, is the synthesis and coordination chemistry of seven novel ligands L1 - L7. These ligands form metallosupramolecular assemblies upon coordination of transition metal ions resulting in heterodi- and hetreotrimetallic double helicates and penta- and tetranuclear cyclic helicates. Described in Chapter 2 is a new class of ditopic segmental pyridyl-thiazole(py-tz) N-donor ligands L1 - L3. Reaction of L1 with ZnII ions results in the formation of a dinuclear double helicate [Zn2(L1)2]4+. Reaction of L2 with either ZnII or HgII results in the formation of the L2-containing dinuclear double helicates [Zn2(L2)2]4+ and [Hg2(L2)2]4+. However, reaction with both ZnII or HgII results in the sole formation of the heterodimetallic helicate [HgZn(L2)2]+. Both metal ions are 6-coordinate but the HgII ion is coordinated by the two py-tz-py units whereas the ZnII ion is coordinated by the py-py-tz domain. The reason that these isomeric sites have different preferences for each of the metal ions is due to the position of the thiazole unit within the terdentate domains, as in the central position the thiazole unit increases the?bite angle? of the donor unit making it more suitable for the larger HgII. Conversely the py-py-tz domain has a smaller bite angle and it more suited to the smaller ZnII ion. Reaction of L3 with ZnII, HgII and CuII results in the formation of a heterometallic trinuclear double helicate [HH-[HgCuZn(L3)2]5+. In a similar fashion to L2, the ZnII ion coordinated by the terdentate py-py-tz domain and the HgII coordinated by the py-tz-py domain. The central bipyridine unit coordinates the tetrahedral CuII ion resulting in the first reported example of a heterotrimetallic double helicate. Described in Chapter 4 is a potentially hexadentate N-donor ligand L4, which upon reaction with CdII results in the formation of a dinuclear double helicate [Cd2(L4)2]4+. In this structure the ligand partitions into two tridentate tz-py-py domains each of which coordinate a different metal ion. However, reaction of L4 with ZnII results in the formation of a pentanuclear circular helicate [Zn5(L4)5]10+, with all the five zinc ions adopting a octahedral coordination geometry arising from the coordination of the two tridentate tz-py-py domains from two different ligand strands. This difference in structure is attributed to unfavourable steric interactions which prevent the formation of [Zn2(L4)2]4+ but these unfavourable interactions are not present with the larger Cd2+ ion. Described in Chapter 5 are the potentially pentadentate and tetradentate ligands L5 and L6, respectively. The ligand L5 contains both a bidentate and tridentate binding site separated by a phenylene spacer unit. Reaction of L5 with CuII results in the formation of a pentanuclear circular helicate [Cu5(L5)5]10+. Each of the CuII ions adopts a 5-coordinate geometry formed by coordination of the bidentate domain of one ligand strand and the tridentate domain of a different ligand. As a result this gives a head-to-tail pentanuclear double helicate. Reaction of L6 and L4 (Chapter 4) with CuII results in the formation of a heteroleptic pentanuclear circular helicate [Cu5(L4)3(L6)2]10+. The cyclic array consists of five copper(II) ions, coordinated by three strands of L4 and two strands of L6. In this species four of the CuII adopt a 5- coordinate geometry arising from coordination of a tridentate domain from L4 and a bidentate domain from L6. The remaining copper ion is coordinated by two tridentate domains from L4 resulting in an octahedral coordination geometry. Described in Chapter 6 is the potentially hexadentate N-donor ligand L7 which comprises of two identical tridentate py-py-tz N3 binding domains separated by a pyrene unit. Reaction of L7 with ZnII results in the formation of a tetranuclear circular helicate [Zn4(L7)4]8+ with all four zinc metal ions adopting a six-coordinate geometry arising from the coordination of two tridentate pypy- tz units from two different ligand strands. The formation of this lower nuclearity species (e.g. tetranuclear rather than pentanuclear) is attributed to the p-stacking between the pyrene unit and the py-py-tz domain.
Author: Rebecca Valerie Fennessy
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Languages : en
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Author: Linda Farber
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Category :
Languages : en
Pages : 58
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Author: NILOOFAR. ZARRABI
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Languages : en
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Author: Pekka Hänninen
Publisher: Springer Science & Business Media
ISBN: 3642210236
Category : Science
Languages : en
Pages : 392
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Lanthanides have fascinated scientists for more than two centuries now, and since efficient separation techniques were established roughly 50 years ago, they have increasingly found their way into industrial exploitation and our everyday lives. Numerous applications are based on their unique luminescent properties, which are highlighted in this volume. It presents established knowledge about the photophysical basics, relevant lanthanide probes or materials, and describes instrumentation-related aspects including chemical and physical sensors. The uses of lanthanides in bioanalysis and medicine are outlined, such as assays for in vitro diagnostics and research. All chapters were compiled by renowned scientists with a broad audience in mind, providing both beginners in the field and advanced researchers with comprehensive information on on the given subject.
Author: Marcello De De Falco
Publisher: Springer Science & Business Media
ISBN: 1447151194
Category : Business & Economics
Languages : en
Pages : 202
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As the annual production of carbon Dioxide (CO2) reaches 30 billion tones, the growing issue of the greenhouse effect has triggered the development of technologies for CO2 sequestration, storage and use as a reactant. Collecting together the reports of the Congress at University of Rome (Campus Bio-medico) held 16th April 2012, CO2: A Valuable Source of Carbon presents and discusses promising technologies for the industrial exploitation of CO2. Divided into two parts, the current technology is evaluated and summarized before European and national projects are presented. The focus on CO2 recovery, particularly in value-added production, proposes applicable methods to develop sustainable practices and even to mitigate greenhouse gas emission from large-scale fossil fuels usage. Including current data and real-world examples, CO2: A valuable source of carbon provides students, engineers, researchers and industry professional with up-to-date material and potential areas for development and research.
Author: Ramon Vilar
Publisher: Springer Science & Business Media
ISBN: 3540790918
Category : Science
Languages : en
Pages : 261
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This book presents critical reviews of the present position and future trends in modern chemical research concerned with chemical structure and bonding. The book contains short and concise reports, each written by the world's renowned experts.
Author: Catherine E. Housecroft
Publisher: MDPI
ISBN: 3036514635
Category : Science
Languages : en
Pages : 264
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This Special Issue is one of the first for the new MDPI flagship journal Chemistry (ISSN 2624-8549) which has a broad remit for publishing original research in all areas of chemistry. The theme of this issue is Supramolecular Chemistry in the 3rd Millennium and I am sure that this topic will attract many exciting contributions. We chose this topic because it encompasses the unity of contemporary pluridisciplinary science, in which organic, inorganic, physical and theoretical chemists work together with molecular biologists and physicists to develop a systems-level understanding of molecular interactions. The description of supramolecular chemistry as 'chemistry beyond the molecule' (Jean-Marie Lehn, Nobel Lecture and Gautam R. Desiraju, Nature, 2001, 412, 397) addresses the wide variety of weak, non-covalent interactions that are the basis for the assembly of supramolecular architectures, molecular receptors and molecular recognition, programed molecular systems, dynamic combinatorial libraries, coordination networks and functional supramolecular materials. We welcome submissions from all disciplines involved in this exciting and evolving area of science.
Author: Hani Amouri
Publisher: John Wiley & Sons
ISBN: 047072160X
Category : Science
Languages : en
Pages : 260
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Chirality in Transition Metal Chemistry is an essential introduction to this increasingly important field for students and researchers in inorganic chemistry. Emphasising applications and real-world examples, the book begins with an overview of chirality, with a discussion of absolute configurations and system descriptors, physical properties of enantiomers, and principles of resolution and preparation of enantiomers. The subsequent chapters deal with the the specifics of chirality as it applies to transition metals. Some reviews of Chirality in Transition Metal Chemistry "...useful to students taking an advanced undergraduate course and particularly to postgraduates and academics undertaking research in the areas of chiral inorganic supramolecular complexes and materials." Chemistry World, August 2009 “...the book offers an extremely exciting new addition to the study of inorganic chemistry, and should be compulsory reading for students entering their final year of undergraduate studies or starting a Ph.D. in structural inorganic chemistry.” Applied Organometallic Chemistry Volume 23, Issue 5, May 2009 “...In conclusion the book gives a wonderful overview of the topic. It is helpful for anyone entering the field through systematic and detailed introduction of basic information. It was time to publish a new and topical text book covering the important aspect of coordination chemistry. It builds bridges between Inorganic, organic and supramolecular chemistry. I can recommend the book to everybody who is interested in the chemistry of chiral coordination compounds .” Angew. chem. Volume 48, Issue 18, April 2009 About the Series Chirality in Transition Metal Chemistry is the latest addition to the Wiley Inorganic Chemistry Advanced Textbook series. This series reflects the pivotal role of modern inorganic and physical chemistry in a whole range of emerging areas such as materials chemistry, green chemistry and bioinorganic chemistry, as well as providing a solid grounding in established areas such as solid state chemistry, coordination chemistry, main group chemistry and physical inorganic chemistry.
