CHAN-FUNG. LAM
Published: 2017-01-26
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This dissertation, "Synthesis, Optical and Luminescence Studies of Rhenium(I) Diimine Alkynyl Complexes and Their Utilization as Building Blocks for the Assembly of Multinuclear and Mixed-metal Complexes" by Chan-fung, Lam, 林親鳳, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled SYNTHESIS, OPTICAL AND LUMINESCENCE STUDIES OF RHENIUM(I) DIIMINE ALKYNYL COMPLEXES AND THEIR UTILIZATION AS BUILDING BLOCKS FOR THE ASSEMBLY OF MULTINUCLEAR AND MIXED-METAL COMPLEXES submitted by LAM Chan Fung for the degree of Doctor of Philosophy at The University of Hong Kong in July 2005 A series of mononuclear rhenium(I) diimine complexes with hyperbranched or functional alkynyl ligands, [C H -1,3-(HC C C H C C) -5-{Re(CO) (N N)(C C 6 3 6 4 2 3 t C H C C)}] (N N = bpy, Bu bpy) and [Re(CO) (N N)(C C C C R)] (R = C H I-p, 6 4 2 3 6 4 C H C C SiMe -p, CHC C H-p, C H OSiMe Bu-p, CHOH-p) have been 6 4 3 6 4 6 4 2 6 4 synthesized. The X-ray crystal structures of [CH-1,3-(HCCCHCC)-5-{Re(CO)(Bubpy)(CCCHCC)}] and 63 64 2 32 64 [Re(CO)(Bubpy)(CCCCCHCCH-p)] have been presented. By employing 32 64 [Re(CO) (N N)(C C C C C H I-p)] as a precursor, a series of dinuclear rhenium(I) 3 6 4 alkynyl complexes with extended conjugation, [Re(CO) (N N)(C CC C C H C C 3 6 4 t (C H ) C C C H C CC C)Re(CO) (N N)] [n = 0, 1; N N = Bu bpy, (CF ) bpy], 6 4 n 6 4 3 2 3 2 have been prepared. Additionally, a series of symmetrical and unsymmetrical trinuclear rhenium(I) alkynyl complexes, [C H -1,3,5-{Re(CO) (N N)(C C C C 6 3 3 t t C H C C)} ] [N N = Bu bpy, (CF ) bpy] and [C H -1,3-{Re(CO) (Bu bpy)(C C 6 4 3 2 3 2 6 3 3 2 C C C H C C C H C C)} -5-{Re(CO) ( Bu bpy)(C C C H C C)}], have also 6 4 6 4 2 3 2 6 4 been synthesized. The lowest-lying excited states of these complexes were 3 3 tentatively assigned as admixture of MLCT[d (Re) *(N N)], LLCT[ (C C R) 3 *(N N)] and IL[ (C C R) *(C C R)] origin. Besides, a series of luminescent heterometallic rhenium(I) palladium(II) t complexes, trans-[Pd(PEt ) Cl{(C C Ar C C)Re(CO) (N N)}] (N N = bpy, Bu bpy; 3 2 3 2 Ar = C H S, C H ) and trans-[Pd(PEt ) {(C C C H C C)Re(CO) ( Bu bpy)} ], have 4 2 6 4 3 2 6 4 3 2 2 been synthesized. The X-ray crystal structures of t trans-[Pd(PEt)Cl{(CCCHCC)Re(CO)(N N)}] (N N = bpy, Bu bpy) have been 32 64 3 2 determined. Their emission was attributed to MLCT[d (Re) *(N N)] 3 phosphorescence mixed with LLCT[ (C C R) *(N N)] character. A lower emission energy for the hetero-bimetallic complex was observed upon coordination of the electron-rich palladium(II) moiety into the rhenium(I) alkynyl system. However, replacement of the remaining chloro group on the palladium centre with an additional rhenium(I) alkynyl moiety resulted in a higher energy emission for the hetero-trimetallic complex. A series of luminescent heterometallic rhenium(I) platinum(II) phosphine complexes, [{Re(CO)(NN)(CCCHCC)}Pt(PP)] [PP = dppe, depe, 3 6 4 2 t cis-(PEt), trans-(PEt ); N N = Bu bpy, (CF ) bpy], have been synthesized. The 32 3 2 2 3 2 X-ray crystal structure of [{Re(CO){(CF)bpy}(C C CH C C)}Pt(dppe)] has 3 3 2 6 4 2 been determined. The emission was ascribed as derived from states of a [d (Re) 3 3 *(N N)] MLCT origin that mixed with LLCT[ (C C R) *(N N)] character; or alternatively, as an excited state of a [ {C C C H C C Pt(P P)} *(N N)] 6 4 metalloligand-to-ligand charge transfer character. Another new class of luminescent heterometallic rhenium(I)platinum(II) polypyridine alkynyl complexes, t [Re
