Premium
Phosphorescence Color Alteration by Changing Counter Anions on Tetrahedral Gold(I) Complexes; Intra‐ and Interligand π–π Interactions
Author(s) -
Osawa Masahisa,
Kawata Isao,
Igawa Satoshi,
Tsuboyama Akira,
Hashizume Daisuke,
Hoshino Mikio
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900483
Subject(s) - chemistry , phosphorescence , crystallography , density functional theory , crystal (programming language) , crystal structure , ion , photochemistry , computational chemistry , organic chemistry , fluorescence , physics , quantum mechanics , computer science , programming language
Tetrahedral gold(I) complexes containing the diphosphaneligand [dppb = 1,2‐bis(diphenylphosphanyl)benzene], [Au(dppb) 2 ]X {X = Cl ( 1 ), BF 4 ( 2 ) and PF 6 ( 3 )}, were prepared and characterized by X‐ray structural analysis. Complexes 1 and 2 have almost the same structure with two dppb ligands, which are symmetrically coordinated to the Au atom in the crystal. However, the two dppb ligands of 3 are asymmetrically bound to the gold(I) stom in the crystal. Both colorless complexes 1 and 2 exhibit intense blue phosphorescence with peak maxima at 481 nm ( Φ p = 0.86) for 1 and 490 nm ( Φ p = 0.90) for 2 , respectively. The pale yellow complex 3 shows weak yellow‐orange phosphorescence with a peak maximum at 596 nm ( Φ p = 0.04). A small conformational change in the crystal, which is caused by changing the counter anion, dramatically alters the optical properties of the tetrahedral gold(I) complexes in the solid state. The difference in the absorption and phosphorescence spectra between 1 and 3 has been interpreted on the basis of molecular arrangement including packing structures of the complexes and time‐dependent density functional theory (TD‐DFT) calculations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)