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Metal Chalcogenide Nanocrystal Assembly: From Synthesis To Applications, Qinghong Yao

Wayne State University Dissertations

This dissertation study is focused on (1) the application of an oxidation-induced sol-gel assembly method to formation of CdTe aerogels; (2) extension of existing aerogel compositions and properties by an alternative synthetic approach: cation-exchange reactions; and (3) probing the functionality of CdSe aerogels as optical sensors of Lewis base analytes.

Highly porous CdTe aerogels were successfully synthesized by sol-gel assembly of CdTe nanocrystals with thiolate or nonthiolate (phosphine oxide) ligated surfaces by treatment with tetranitromethane. Both phosphine oxide-capped and the thiolate-capped aerogels exhibit similar structure, morphology and porosimetry properties, suggesting that precursor ligation does not have a no major effect …

Synthesis And Characterization Of Metal Complexes Containing Tetrazolate, Poly(Tetrazolyl)Borate, And Aryl Pentazole Ligands As High Energy Density Materials, Dongmei Lu

Wayne State University Dissertations

Heavier alkaline earth metal tetrazolates have been prepared as cryatals contain aqua ligands and as anhydrous powders, and were characterized by spectral and analytical methods. Potassium bis(tetrazolyl)borate complexes K(BH₂(RCN₄)₂)(H₂O)_n (R = H, Me, NMe₂, and NiPr₂) and their 18-crown-6 adducts have been synthesized. In the solid state, complexes where R = H and Me have B-N bonds to the nitrogen atoms proximal to the carbon atom, whereas those with R = NMe₂ and NiPr₂ possess isomeric B-N bonds to the nitrogen atoms distal to the …

Experimental And Theoretical Analysis Of The Electronic Behavior In Five-Coordinate Iron(Iii) And Six-Coordinate Cobalt(Iii) Complexes With Electroactive Phenol-Rich Ligands, Marco Mathieu Allard

Wayne State University Dissertations

Three 5 coordinate high-spin Iron(III) complexes containing pentadentate N2O5 ligands were synthesized and characterized, namely, (1) [FeIII(L1)] and (2) [FeIII(L2)]. Structural differences in ligand design,N,N,N'-tris(3,5-di-tert-butyl-2-hydroxybenzyl)benzene-1,2-diamine for (1) and N,N,N'-tris-(3,5-di-tert-butyl-2-hydroxybenzyl)-N'-methyl-benzene-1,2-diamine for (2), result in complexes that due to their forced geometry, asymmetry, and slightly different electronic structures are able to foster phenoxyl radicals although show a sensitive dependence to both the solvent and the electrolyte system in the cyclic voltammetry. In the presence of TBAClO4 (1) exhibits a two-electron oxidation, whereas in the presence of TBAPF6 (2), , shows three distinct phenolato/phenoxyl radical couples. Both (1) and (2) were redox-cycled 30 …

The Synthesis, Structure, And Properties Of Group 2 Poly(Pyrazolyl)Borates And Their Use For The Atomic Layer Deposition Of Group 2 Borates, Mark J. Saly

Wayne State University Dissertations

A series of heavy alkaline earth complexes containing TpR2-based ligands has been synthesized, structurally characterized, and their properties were investigated. Salt metathesis routes involving MI2 (M = Ca, Sr, Ba) with either KTpEt2 or KTpnPr2 afforded MTpEt22 or MTpnPr22 in good to moderate yields. All of these complexes are volatile and exceptionally thermally stable, and have acceptable properties for use as group 2 atomic layer deposition (ALD) precursors. In addition, a series of group 2 complexes containing BpR2-based ligand systems were synthesized. Treatment of MI2 (M = Ca, Sr, Ba) with two equivalents of TlBptBu2, KBp, and KBpiPr2 in tetrahydrofuran …

Synthetic Levers Enabling Control Of Phase, Size And Morphology In Transition Metal Phosphide Nanoparticles (Fe, Ni), Elayaraja Muthuswamy

Wayne State University Dissertations

ABSTRACT

SYNTHETIC LEVERS ENABLING CONTROL OF PHASE, SIZE AND MORPHOLOGY IN TRANSITION METAL PHOSPHIDE NANOPARTICLES (FE, NI)

by

ELAYARAJA MUTHUSWAMY

May 2011

Advisor:Dr. Stephanie L. Brock

Major: Chemistry

Degree: Doctor of Philosophy

This dissertation study focuses on (1) development of a synthetic strategy to control phase in nanoscale iron phosphides; (2) extension of the developed phase control strategy to the nanoscale nickel phosphide system with simultaneous control on size and morphology and (3) illustration of the enhanced reactivity of nanoscale oxide systems.

A synthetic strategy to control phase in nanoscale iron phosphides was developed to prepare phase-pure samples of …