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Synthesis and photophysics of bis-cy...

Murphy, Drew Logan.

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Synthesis and photophysics of bis-cyclometalated iridium(III) complexes for use in organic light emitting devices and singlet oxygen sensitization.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Synthesis and photophysics of bis-cyclometalated iridium(III) complexes for use in organic light emitting devices and singlet oxygen sensitization./
作者:	Murphy, Drew Logan.
面頁冊數:	174 p.
附註:	Source: Dissertation Abstracts International, Volume: 65-11, Section: B, page: 5717.
Contained By:	Dissertation Abstracts International65-11B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3155455
ISBN:	0496162306

Synthesis and photophysics of bis-cyclometalated iridium(III) complexes for use in organic light emitting devices and singlet oxygen sensitization.
Murphy, Drew Logan.

Synthesis and photophysics of bis-cyclometalated iridium(III) complexes for use in organic light emitting devices and singlet oxygen sensitization. - 174 p.

Source: Dissertation Abstracts International, Volume: 65-11, Section: B, page: 5717.

Thesis (Ph.D.)--University of Southern California, 2004.

The synthesis, photophysics, and singlet oxygen sensitization properties of octahedral organometallic iridium complexes with several different cyclometalated ligands are reported. Iridium trichloride cleanly cyclometalates a number of different compounds (i.e., 2-phenylbenzothiazole, 2-phenylbenzimidazole, 2-phenylbenzoxazole, 3,3-dimethyl-2-phenyl-3H-indole, 2-phenylquinoline, and other phenylquinoline and naphthylpyridine isomers), forming the corresponding chloride-bridged dimers, (C^N)2Ir(mu-Cl)2Ir(C^N)2 (C^N is a cyclometalatedligand) in good yield. These chloride-bridged dimers react with 2,4-pentanedione (acacH) and other lewis basic ligands such as picolinic acid, pyridine, phenanthrolines, 2,2'-bibpyridine, glycine, etc., to give monomeric (C^N)2Ir(LX) complexes (LX = ancillaryligand(s)). The emission spectra of these complexes are largely governed by the nature of the cyclometalating ligand, leading to lambdamax values from 500 to 685 nm for the complexes reported here. The strong spin-orbit coupling of iridium mixes the formally forbidden 3MLCT and 3(pi-pi*) transitions with the allowed 1MLCT, leading to a strong phosphorescence with good quantum efficiencies (0.1--0.8) and room temperature lifetimes in the microsecond regime. These complexes were also examined as potential singlet oxygen sensitizers. The luminescence from these complexes is quenched by molecular oxygen at near diffusion controlled rates (2.9--7.2 x 109 M-1s -1). This quenching does lead to efficient production of singlet oxygen by these complexes, with quantum yields of singlet oxygen production (phiDelta) at least as large as the standard sensitizers (0.54--1.00). These iridium(III) complexes were also examined for quenching of the produced singlet oxygen. The rates of quenching of singlet oxygen were three orders of magnitude slower than those for quenching of the luminescence by molecular oxygen (0.5--6.3 x 106 M-1s -1). In efforts to red shift the absorbance of these iridium complexes, larger aromatic ligands were synthesized (ie. 1-(1-Naphthyl)isoqunoline (11nq) and 1-aza-perylene (1ap)). Due to steric strain the 11nq is twisted 63°, while the lap is perfectly planar. This is exhibited in both the absorption and emission spectra (lambdamax, abs 282 and 443 nm, respectively; lambdamax, em 362 and 451 nm, respectively). Removing the twist of 11nq by oxidizing it to 1ap also increases the quantum yield from 0.005 to 0.66. Preliminary results suggest that these photophysical characteristics are also present in their beta-diketonate complexes.

ISBN: 0496162306Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Synthesis and photophysics of bis-cyclometalated iridium(III) complexes for use in organic light emitting devices and singlet oxygen sensitization.
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500 $a Adviser: Mark E. Thompson.
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