En Route to the Formation of High-Efficiency, Osmium(II)-Based Phosphorescent Materials
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- 作者：Fang-Chi Hsu ; Yung-Liang Tung ; Yun Chi ; Cheng-Chih Hsu ; Yi-Ming Cheng ; Mei-Lin Ho ; Pi-Tai Chou ; Shie-Ming Peng ; Arthur J. Carty
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：December 11, 2006
- 年：2006
- 卷：45
- 期：25
- 页码：10188 - 10196
- 全文大小：251K
- 年卷期：v.45,no.25(December 11, 2006)
- ISSN：1520-510X
文摘
Triosmium cluster complexes [Os3(CO)8(fppz)2] (2a) and [Os3(CO)8(fptz)2] (2b) bearing two 2-pyridyl azolate ligandswere synthesized in an attempt to establish the reaction mechanism that gives rise to the blue-emitting phosphorescentcomplexes [Os(CO)2(fppz)2] (1a) and [Os(CO)2(fptz)2] (1b) [(fppz)H = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole; (fptz)H= 3-(trifluoromethyl)-5-(2-pyridyl)triazole]. X-ray structural analysis of 2b showed an open triangular metal frameworkincorporating multisite-coordinated 2-pyridyltriazolate ligands. Treatment of 2 with the respective 2-pyridylazolateligand led to the formation of blue-emitting complex 1b, confirming their intermediacy, while the reaction of 2b withphosphine ligand PPh2Me afforded two hitherto novel hydride complexes 3 and 4, for which the reversibleinterconversion was clearly established at higher temperatures (>180 
C). The single-crystal X-ray diffraction analysesof 3 and 4 confirmed their monometallic and isomeric nature, together with the coordination of two phosphineligands located in the trans-disposition and one CO and one hydride located opposite to the pyridyl triazolatechelate. Subtle differences in photophysical properties were examined for isomers 3 and 4 on the basis of steadystate absorption and emission, the relaxation dynamics, and temperature-dependent luminescent studies. The results,in combination with time-dependent density function theory (TDDFT) calculations, provide fundamental insights intothe future design and preparation of highly efficient phosphorescent emitters.
C). The single-crystal X-ray diffraction analysesof 3 and 4 confirmed their monometallic and isomeric nature, together with the coordination of two phosphineligands located in the trans-disposition and one CO and one hydride located opposite to the pyridyl triazolatechelate. Subtle differences in photophysical properties were examined for isomers 3 and 4 on the basis of steadystate absorption and emission, the relaxation dynamics, and temperature-dependent luminescent studies. The results,in combination with time-dependent density function theory (TDDFT) calculations, provide fundamental insights intothe future design and preparation of highly efficient phosphorescent emitters.