Thesis (Ph. D.)--University of Chicago. / From the American chemical journal, v. 36. Includes bibliographical references. Also available on the Internet.

Thesis (PH.D.)--University of Chicago. / From the American chemical journal, v. 36. Includes bibliographical references. Also available on the Internet.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Thesis (Ph. D.)--University of Hong Kong, 1998. / Includes bibliographical references (leaf 300-330).

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

This thesis describes the synthesis and characterisation of a variety of acetylide-bridged di- and trinuclear ruthenium acetylide complexes that were prepared in a controlled fashion, and the preparation and characterisation of the ruthenium(II) complexes required for these stepwise reactions. These precursor complexes, or building blocks, include dimethyl-, acetylidomethyl-, and bis(acetylido)ruthenium(II) complexes. An introduction to metal acetylide chemistry is presented in Chapter 1. The previous research in this area is briefly reviewed, and the potential applications of these complexes are highlighted. The primary aims of this course of work are outlined, namely, to develop a controlled synthetic approach to the synthesis of oligonuclear ruthenium acetylide complexes. The synthetic strategies for this aim are introduced in Chapter 2, and the synthetic routes to cis and trans-Ru(CH3)2(dmpe)2 (25/23) and cis and trans-Ru(CH3)2(depe)2 (26/24) are described. Characterisation of the novel, synthetically important trans-Ru(CH3)2(dmpe)2 (23) is completed by an examination of its X-Ray crystallographic structure. Chapter 3 describes the thermal and photochemical metathesis reactions of trans-Ru(CH3)2(dmpe)2 (23) with terminal acetylenes, and the preparation of a variety of acetylidomethylruthenium(II) complexes, trans-Ru(CH3)(C≡CR)(dmpe)2 (R = Ph (30), tBu (31), SiMe3 (32), C6H4-4-tBu (33), C6H3-3,5-tBu2 (34), C6H4-4-C≡CH (35), C6H4-4-OCH3 (36), C6H4-4-CH3 (37), C6H3-3,5-(CF3)2 (38)). The characterisation of these complexes by NMR spectroscopy, IR spectroscopy and X-Ray crystallography is presented. A clean and high yielding synthesis of the synthetically significant unsymmetrical bis(acetylido)ruthenium(II) complexes was developed via the reaction of an acetylidomethylruthenium(II) complex with an excess of a second terminal alkyne in a mixture of methanol and benzene. The characterisation of the novel complexes trans-Ru(C≡CR)(C≡CR′)(dmpe)2 (R = Ph, R′ = tBu (40), SiMe3 (41), C6H4-4-C≡CH (44); R = tBu, R′ = SiMe3 (42), C6H4-4-C≡CH (43), C6H4-4-tBu (45), C6H3-3,5-tBu2 (46)) by NMR and IR spectroscopy, mass spectrometry and X-Ray crystallography is described in Chapter 4. Additionally, Chapter 4 describes the synthesis and characterisation of symmetrical bis(acetylido)ruthenium(II) complexes, and a number of organic butenyne compounds, which were observed as by-products from the attempted synthesis of several of the bis(acetylido)ruthenium(II) complexes. Dinuclear ruthenium(II) complexes were prepared by the reaction of trans-Ru(C≡CR)(C≡CC6H4-4-C≡CH)(dmpe)2 (R = tBu (43) or Ph (44)) with an acetylidomethylruthenium(II) complex in toluene and methanol. Both symmetrical and unsymmetical dinuclear complexes could be prepared in this way, and were characterised by a range of techniques including NMR spectroscopy, IR spectroscopy, mass spectrometry and X-Ray crystallography, and are described in Chapter 5. In addition, an electrochemical study of one of the dinuclear complexes was undertaken using cyclic voltammetry. The symmetrical trinuclear ruthenium(II) complexes, trans,trans,trans- (RC≡C)Ru(dmpe)2(μ-C≡CC6H4C≡C)Ru(depe)2(μ-C≡CC6H4C≡C)Ru(dmpe)2(C≡CR) (R = Ph (80), tBu (81), SiMe3 (82)) was prepared by the reaction of two equivalents of an acetylidomethylruthenium(II) complex with the symmetrical bis(acetylido)ruthenium(II) complex, trans-Ru(C≡CC6H4-4-C≡CH)2(depe)2 (54), in toluene and methanol. These syntheses, and the subsequent characterisation of the products are also reported in Chapter 5. The primary aim of this thesis, viz. the synthesis and characterisation of acetylide bridged di- and trinuclear ruthenium acetylide complexes in a controlled fashion, was successfully achieved. Suggestions for future work are described in Chapter 6.

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

This thesis describes the synthesis and characterisation of a variety of acetylide-bridged di- and trinuclear ruthenium acetylide complexes that were prepared in a controlled fashion, and the preparation and characterisation of the ruthenium(II) complexes required for these stepwise reactions. These precursor complexes, or building blocks, include dimethyl-, acetylidomethyl-, and bis(acetylido)ruthenium(II) complexes. An introduction to metal acetylide chemistry is presented in Chapter 1. The previous research in this area is briefly reviewed, and the potential applications of these complexes are highlighted. The primary aims of this course of work are outlined, namely, to develop a controlled synthetic approach to the synthesis of oligonuclear ruthenium acetylide complexes. The synthetic strategies for this aim are introduced in Chapter 2, and the synthetic routes to cis and trans-Ru(CH3)2(dmpe)2 (25/23) and cis and trans-Ru(CH3)2(depe)2 (26/24) are described. Characterisation of the novel, synthetically important trans-Ru(CH3)2(dmpe)2 (23) is completed by an examination of its X-Ray crystallographic structure. Chapter 3 describes the thermal and photochemical metathesis reactions of trans-Ru(CH3)2(dmpe)2 (23) with terminal acetylenes, and the preparation of a variety of acetylidomethylruthenium(II) complexes, trans-Ru(CH3)(C≡CR)(dmpe)2 (R = Ph (30), tBu (31), SiMe3 (32), C6H4-4-tBu (33), C6H3-3,5-tBu2 (34), C6H4-4-C≡CH (35), C6H4-4-OCH3 (36), C6H4-4-CH3 (37), C6H3-3,5-(CF3)2 (38)). The characterisation of these complexes by NMR spectroscopy, IR spectroscopy and X-Ray crystallography is presented. A clean and high yielding synthesis of the synthetically significant unsymmetrical bis(acetylido)ruthenium(II) complexes was developed via the reaction of an acetylidomethylruthenium(II) complex with an excess of a second terminal alkyne in a mixture of methanol and benzene. The characterisation of the novel complexes trans-Ru(C≡CR)(C≡CR′)(dmpe)2 (R = Ph, R′ = tBu (40), SiMe3 (41), C6H4-4-C≡CH (44); R = tBu, R′ = SiMe3 (42), C6H4-4-C≡CH (43), C6H4-4-tBu (45), C6H3-3,5-tBu2 (46)) by NMR and IR spectroscopy, mass spectrometry and X-Ray crystallography is described in Chapter 4. Additionally, Chapter 4 describes the synthesis and characterisation of symmetrical bis(acetylido)ruthenium(II) complexes, and a number of organic butenyne compounds, which were observed as by-products from the attempted synthesis of several of the bis(acetylido)ruthenium(II) complexes. Dinuclear ruthenium(II) complexes were prepared by the reaction of trans-Ru(C≡CR)(C≡CC6H4-4-C≡CH)(dmpe)2 (R = tBu (43) or Ph (44)) with an acetylidomethylruthenium(II) complex in toluene and methanol. Both symmetrical and unsymmetical dinuclear complexes could be prepared in this way, and were characterised by a range of techniques including NMR spectroscopy, IR spectroscopy, mass spectrometry and X-Ray crystallography, and are described in Chapter 5. In addition, an electrochemical study of one of the dinuclear complexes was undertaken using cyclic voltammetry. The symmetrical trinuclear ruthenium(II) complexes, trans,trans,trans- (RC≡C)Ru(dmpe)2(μ-C≡CC6H4C≡C)Ru(depe)2(μ-C≡CC6H4C≡C)Ru(dmpe)2(C≡CR) (R = Ph (80), tBu (81), SiMe3 (82)) was prepared by the reaction of two equivalents of an acetylidomethylruthenium(II) complex with the symmetrical bis(acetylido)ruthenium(II) complex, trans-Ru(C≡CC6H4-4-C≡CH)2(depe)2 (54), in toluene and methanol. These syntheses, and the subsequent characterisation of the products are also reported in Chapter 5. The primary aim of this thesis, viz. the synthesis and characterisation of acetylide bridged di- and trinuclear ruthenium acetylide complexes in a controlled fashion, was successfully achieved. Suggestions for future work are described in Chapter 6.

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

Title page, abstract and table of contents only. The complete thesis in print form is available from the University of Adelaide Library. / With the increasing use of lasers it is necessary to develop materials that can provide protection to eyes and other sensitive devices. This thesis reports on an investigation into optical limiting of Transition Metal Acetylides (TMAs) that transmit ambient light levels of light but block high energy (laser) light across the visible part of the spectrum. A standard optical limiting testbed is used to measure opt~callimiting at 470, 532 and 630 om for a wide range of Pt:ethynyl related TMAs. I report the effect on optical limiting of altering the central bridge, heavy metal, terminal group, solubilising group and oligomerisation. Most of these materials showed poor optical limiting, especially in the red. Two dimers of Pt:ethynyl, however, have clamping levels at 532 om better than that for Pt:ethynyl. I therefore describe a detailed spectroscopic investigation of two series of oligomers and discuss their structure/property relationships. This investigation also includes a precursor ofPtethynyl, PEPE, which shows remarkable limiting. I also report modelling of optical limiting using a 5-level model constructed using the spectroscopic data. I show that the 5-level model can be validated and accurately predicts the limiting for PEPE against both ps and ns pulses. It can also be used to predict ps limiting for Pt:ethynyl and its oligomers. For ns pulses, however, it predicts much less limiting than that observed. I therefore propose a new mechanism that is important for ns limiting by TMAs. Finally I discuss the broadband limiting of these materials and from analysis of the measurements· I describe structures of materials that may show promising broadband optical limiting. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320307 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008