Acta Phys. -Chim. Sin. ›› 2009, Vol. 25 ›› Issue (10): 2113-2117.doi: 10.3866/PKU.WHXB20090936

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The Lowest Triplet Excited States of Ph3PAuXand Ph3AsAuX(X=Cl, Br)

MANG Chao-Yong, ZI Jun-Qing, ZHAO Xia, WU Ke-Chen   

  1. College of Life Science and Chemistry, Dali University, Dali 671000, Yunnan Province, P. R. China|Institute of Eastern-Himalaya Biodiversity Research, Dali University, Dali 671000, Yunnan Province, P. R. China|State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China
  • Received:2009-03-04 Revised:2009-06-11 Published:2009-09-29
  • Contact: MANG Chao-Yong, WU Ke-Chen;


A reasonable interpretation of multi-color luminescence mechanisms for molecular materials can be obtained from theoretical research into molecular excited states. Molecular structures and photophysical properties of the restricted (T1a) and relaxed (T1b) lowest triplet excited states of four two-coordinated Au(I) complexes, Ph3PAuCl, Ph3PAuBr, Ph3AsAuCl, and Ph3AsAuBr, were investigated using the single-excitation configuration interaction (CIS) method. Because of a remarkable distortion of the θ(PAuX)/θ(AsAuX) from 180°to about 120°, the T1b state was found to be considerably reduced in energy, e.g. 0.805-1.124 eV using CIS, 0.820-0.947 eV using density functional theory (DFT). An analysis of the natural bond orbital (NBO) electronic spin density indicates that two single electrons mostly populate on one of the three phenyls for the T1a state and on the PAuX/AsAuX fragment for the T1b state. Finally, a higher-energy phosphorescence was observed in the crystals and was assigned to one inter-phenyl 3π*→1πtransition of the T1a state, whereas a lower-energy phosphorescence was mostly due to a 3σ*→1σtransition in the T1b state with a sp2 hybridized Au(I).

Key words: Gold complex, Luminescence, Excited state, Single-excitation configuration interaction


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