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Title: Group 15/alkali metal complexes and applications to photoemissive materials
Author: Hopkins, A. D.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2000
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The research presented in this thesis falls into four related areas. The synthetic approach used in all studies was the stepwise deprotonation of primary amines and phosphines with Group 15 dimethylamido reagents to produce heterobimetallic Group 15/alkali metal complexes. The principal aim was to examine the decomposition of these species, potentially into photoemission alkali metal antimonate layers. After an initial introduction (Chapter 1) detailing previous methods of synthesis of imido heterobimetallic complexes and photodiode materials, there follows an experimental section (Chapter 2) in which all the experimental details of the various synthetic studies are collected. Chapter 3 deals with the synthesis and characterisation of a range of heterobimetallic complexes of antimony and heavy alkali metals using the stepwise deprotonation of primary amines. Then presented is the first application of the stepwise deprotonation technique to primary phosphines (Chapter 4), demonstrating a direct comparison with heterometallic imido cages. Also presented is the decomposition of the new phosphinidene complex produced into Zintl compounds, providing a low-temperature route to these species. The applications of a heterometallic Sb/Li phopshinidene complex and an Sb/Li Zintl compound to the formation of photosensitive alloys is investigated and measurements show that photoactive materials are accessible via this route. In Chapter 5 the decomposition of phosphinidene complexes into Zintl compounds is probed. The formation of heterocyclic anions of the type [(RP)nE]- (E=Sb, As) in various reactions of [E(NMe2)3] with [RP(H)Li]n and [RPH2] (R=cyclohexyl, tertiary butyl) suggests that Zintl compounds are generated via these species. In Chapter 6 the study shifts its focus to the synthesis of heterometallic As/alkali metal complexes containing [As2(NCy)4]2- anions (Cy=cyclohexyl) and the investigation of the co-ordination chemistry of this species. The theme of ligand synthesis is continued in Chapter 7, where anionic species containing P-P and P-As frameworks are developed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available