Polynuclear Complexes of Lanthanide Elements and Silver-Exploratory Synthesis and Property Investigation

Persistent Link:
http://hdl.handle.net/10150/195206
Title:
Polynuclear Complexes of Lanthanide Elements and Silver-Exploratory Synthesis and Property Investigation
Author:
Wu, Yinglan
Issue Date:
2009
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:
Polynuclear lanthanide complexes have attracted increasing interest in coordination and materials chemistry as they generally possess aesthetically pleasing molecular structures and display interesting properties possibly for useful chemical and materials applications. The work described herein concerned with the exploratory synthesis, structural characterization, and property investigation of a number of polynuclear lanthanide and silver complexes with selected organic ligands. Details of this thesis work are summarized in the following chapters: Chapter 1 offers a background of the research, with an emphasis on lanthanide-containing compounds and polynuclear silver complexes. Synthetic methodologies, novel structural characteristics, and interesting physical properties toward possible applications are surveyed in order to convey the justification of this thesis work. Chapter 2 describes the design and synthesis, structural characterization of a series of dinuclear lanthanide complexes with 1-(2-pyridylazo)-2-naphthol. The photophysical properties of these complexes pertinent to optical-limiting applications are evaluated. Chapter 3 details the halide-templated assembly of dodecanuclear and pentadecanuclear lanthanide hydroxide complexes featuring histidine as supporting ligand via the ligand-controlled hydrolysis. Salient structural features of these complexes are discussed. Chapter 4 reports the synthesis, structural characterization, and spectroscopic studies of the giant polynuclear lanthanide complexes containing a 60-metal cluster core when threonine was used as the supporting ligand. Carbonate has been identified as a novel anionic template in these clusters. These Ln60 cluster complexes feature a sodalite cage structure with 24 vertex-sharing cubane-like [Ln₄(μ₃-OH) ₄]⁸⁺ units. Their magnetic and optical properties are measured and discussed. Chapter 5 describes the unexpected discovery of a polynuclear silver complex with histidine, first isolated from the reaction of a halide-containing polynuclear lanthanide hydroxide complex and then rationally prepared by using silver nitrate and histidine. A series of analogous silver complexes with other amino acids have subsequently prepared and structurally characterized. Chapter 6 details two silver-amino acid helicates composed of individual helical coordination polymers. Optically pure helicates were obtained by using enantiomerically pure amino acids. While silver-glutamate possesses a double-helical structure, silver-aspartate displays an unprecedented six-strand helical structure. Chapter 7 summarizes the results presented in Chapters 2-6 and elaborates on some future research directions toward which each of these projects may be heading.
Type:
text; Electronic Dissertation
Keywords:
Lanthanide; Polynuclear complexes; Silver
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.titlePolynuclear Complexes of Lanthanide Elements and Silver-Exploratory Synthesis and Property Investigationen_US
dc.creatorWu, Yinglanen_US
dc.contributor.authorWu, Yinglanen_US
dc.date.issued2009en_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.abstractPolynuclear lanthanide complexes have attracted increasing interest in coordination and materials chemistry as they generally possess aesthetically pleasing molecular structures and display interesting properties possibly for useful chemical and materials applications. The work described herein concerned with the exploratory synthesis, structural characterization, and property investigation of a number of polynuclear lanthanide and silver complexes with selected organic ligands. Details of this thesis work are summarized in the following chapters: Chapter 1 offers a background of the research, with an emphasis on lanthanide-containing compounds and polynuclear silver complexes. Synthetic methodologies, novel structural characteristics, and interesting physical properties toward possible applications are surveyed in order to convey the justification of this thesis work. Chapter 2 describes the design and synthesis, structural characterization of a series of dinuclear lanthanide complexes with 1-(2-pyridylazo)-2-naphthol. The photophysical properties of these complexes pertinent to optical-limiting applications are evaluated. Chapter 3 details the halide-templated assembly of dodecanuclear and pentadecanuclear lanthanide hydroxide complexes featuring histidine as supporting ligand via the ligand-controlled hydrolysis. Salient structural features of these complexes are discussed. Chapter 4 reports the synthesis, structural characterization, and spectroscopic studies of the giant polynuclear lanthanide complexes containing a 60-metal cluster core when threonine was used as the supporting ligand. Carbonate has been identified as a novel anionic template in these clusters. These Ln60 cluster complexes feature a sodalite cage structure with 24 vertex-sharing cubane-like [Ln₄(μ₃-OH) ₄]⁸⁺ units. Their magnetic and optical properties are measured and discussed. Chapter 5 describes the unexpected discovery of a polynuclear silver complex with histidine, first isolated from the reaction of a halide-containing polynuclear lanthanide hydroxide complex and then rationally prepared by using silver nitrate and histidine. A series of analogous silver complexes with other amino acids have subsequently prepared and structurally characterized. Chapter 6 details two silver-amino acid helicates composed of individual helical coordination polymers. Optically pure helicates were obtained by using enantiomerically pure amino acids. While silver-glutamate possesses a double-helical structure, silver-aspartate displays an unprecedented six-strand helical structure. Chapter 7 summarizes the results presented in Chapters 2-6 and elaborates on some future research directions toward which each of these projects may be heading.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectLanthanideen_US
dc.subjectPolynuclear complexesen_US
dc.subjectSilveren_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.committeememberWalker, F. Annen_US
dc.contributor.committeememberMiranda, Katrina M.en_US
dc.contributor.committeememberMcGrath, Dominic V.en_US
dc.contributor.committeememberPyun, Jeffreyen_US
dc.identifier.proquest10736en_US
All Items in UA Campus Repository are protected by copyright, with all rights reserved, unless otherwise indicated.