New synthetic and structural chemistry supported by [Re6(u3-Se)8]2+ clusters

Persistent Link:
http://hdl.handle.net/10150/194985
Title:
New synthetic and structural chemistry supported by [Re6(u3-Se)8]2+ clusters
Author:
Tu, Xiaoyan
Issue Date:
2008
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
Transition metal clusters are a unique class of chemical substances. Not only do they have well-defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal-metal bonded species. They may be viewed as atom-like building blocks with adjustable properties. Detailed in this dissertation are the efforts to develop synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability. Specifically, the design and synthesis, structural characterization, and synthetic applications of the cluster complexes of the [Re₆(μ₃-Se)₈]²⁺ core will be discussed. Chapter 1 provides necessary background information of the [Re₆(μ₃-Se)₈]²⁺ core-containing cluster system, the rationales of cluster-supported synthetic and structural chemistry, and the impetus for these endeavors. Chapter 2 details the synthetic applications of stereospecific complexes of the [Re₆(μ₃-Se)₈]²⁺ clusters for the assembly of nanoscopic multicluster arrays using molecular and supramolecular approaches. The synthesis and structural characterization of a triangle-shaped tricluster array and a tetracluster assembly composed of two hydrogen-bonded diclusters are described. Chapters 3 and 4 describe the synthesis of the [Re₆(μ₃-Se)₈]²⁺ core-containing cluster complexes with the water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) ligand and the chemistry of these cluster-complex ligands for the coordination of a variety of secondary metal ions. In Chapter 5, the supramolecular chemistry of the cluster-PTA complexes with Ag(I) is detailed. The coordination of Ag(I) to a cluster complex with two PTA ligands disposed trans- to each other produces a 2-dimensional, porous solid with nano-sized hydrophobic pores that are potentially useful for storage of hydrocarbons and for occlusion of certain substrates for activation and possible catalysis. Chapter 6 summarizes the efforts to synthesize cluster-polymer hybrid materials by using an initiating cluster complex for the controlled radical polymerization. The synthesis, spectroscopic and structural characterizations of a novel cluster complex with an initiating ligand are described. Preliminary results of its application for the controlled polymerization of methyl methacrylate are detailed. Chapter 7 draws a set of conclusions based on the results presented in Chapters 2-6 and elaborates on some future directions aimed at moving one step forward the cluster-supported synthetic and materials chemistry.
Type:
text; Electronic Dissertation
Keywords:
crystal engineering; hexanuclear cluster; hybrid; supramolecular
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Zheng, Zhiping
Committee Chair:
Zheng, Zhiping

Full metadata record

DC FieldValue Language
dc.language.isoENen_US
dc.titleNew synthetic and structural chemistry supported by [Re6(u3-Se)8]2+ clustersen_US
dc.creatorTu, Xiaoyanen_US
dc.contributor.authorTu, Xiaoyanen_US
dc.date.issued2008en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractTransition metal clusters are a unique class of chemical substances. Not only do they have well-defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal-metal bonded species. They may be viewed as atom-like building blocks with adjustable properties. Detailed in this dissertation are the efforts to develop synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability. Specifically, the design and synthesis, structural characterization, and synthetic applications of the cluster complexes of the [Re₆(μ₃-Se)₈]²⁺ core will be discussed. Chapter 1 provides necessary background information of the [Re₆(μ₃-Se)₈]²⁺ core-containing cluster system, the rationales of cluster-supported synthetic and structural chemistry, and the impetus for these endeavors. Chapter 2 details the synthetic applications of stereospecific complexes of the [Re₆(μ₃-Se)₈]²⁺ clusters for the assembly of nanoscopic multicluster arrays using molecular and supramolecular approaches. The synthesis and structural characterization of a triangle-shaped tricluster array and a tetracluster assembly composed of two hydrogen-bonded diclusters are described. Chapters 3 and 4 describe the synthesis of the [Re₆(μ₃-Se)₈]²⁺ core-containing cluster complexes with the water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) ligand and the chemistry of these cluster-complex ligands for the coordination of a variety of secondary metal ions. In Chapter 5, the supramolecular chemistry of the cluster-PTA complexes with Ag(I) is detailed. The coordination of Ag(I) to a cluster complex with two PTA ligands disposed trans- to each other produces a 2-dimensional, porous solid with nano-sized hydrophobic pores that are potentially useful for storage of hydrocarbons and for occlusion of certain substrates for activation and possible catalysis. Chapter 6 summarizes the efforts to synthesize cluster-polymer hybrid materials by using an initiating cluster complex for the controlled radical polymerization. The synthesis, spectroscopic and structural characterizations of a novel cluster complex with an initiating ligand are described. Preliminary results of its application for the controlled polymerization of methyl methacrylate are detailed. Chapter 7 draws a set of conclusions based on the results presented in Chapters 2-6 and elaborates on some future directions aimed at moving one step forward the cluster-supported synthetic and materials chemistry.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectcrystal engineeringen_US
dc.subjecthexanuclear clusteren_US
dc.subjecthybriden_US
dc.subjectsupramolecularen_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorZheng, Zhipingen_US
dc.contributor.chairZheng, Zhipingen_US
dc.contributor.committeememberLichtenberger, Dennis L.en_US
dc.contributor.committeememberMiranda, Katrina M.en_US
dc.contributor.committeememberAspinwall, Craig A.en_US
dc.contributor.committeememberMcGrath, Dominic V.en_US
dc.identifier.proquest10111en_US
dc.identifier.oclc659750514en_US
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