Electronic Excited States of [Au 2 (dmpm) 3 ](ClO 4 ) 2 (dmpm= bis(dimethylphosphine)methane)

作者：King Hung Leung, David Lee Phillips, Zhong Mao, Chi‐Ming Che, Vincent M. Miskowski, C. K. Chan · 发表于：Inorganic Chemistry · 年份：2002 · DOI：10.1021/ic011084v · 被引用次数：33 · 研究领域：Photochemistry and Electron Transfer Studies、Metal complexes synthesis and properties、Organic Light-Emitting Diodes Research

We present studies of the resonance Raman and electronic luminescence spectra of the [Au(2)(dmpm)(3)](ClO(4))(2) (dmpm = bis(dimethylphosphine)methane) complex, including excitation into an intense band at 256 nm and into a weaker absorption system centered about approximately 300 nm. The resonance Raman spectra confirm the assignment of the 256 nm absorption band to a (1)(dsigma --> psigma) transition, a metal-metal-localized transition, in that nu(Au-Au) and overtones of it are strongly enhanced. A resonance Raman intensity analysis of the spectra associated with the 256 nm absorption band gives the ground-state and excited-state nu(Au-Au) stretching frequencies to be 79 and 165 cm(-1), respectively, and the excited-state Au-Au distance is calculated to decrease by about 0.1 A from the ground-state value of 3.05 A. The approximately 300 nm absorption displays a different enhancement pattern, in that resonance-enhanced Raman bands are observed at 103 and 183 cm(-1) in addition to nu(Au-Au) at 79 cm(-1) The compound exhibits intense, long-lived luminescence (in room-temperature CH(3)CN, for example, tau = 0.70 micros, phi(emission) = 0.037) with a maximum at 550-600 nm that is not very medium-sensitive. We conclude, in agreement with an earlier proposal of Mason (Inorg. Chem. 1989, 28, 4366-4369), that the lowest-energy, luminescent excited state is not (3)(dsigma --> psigma) but instead derives from (3)(d(x2-y2,xy --> psigma) excitations. We compare the Au(I)-Au(I) interacti...