The Franck-Condon simulated phosphorescence spectra of Gold(I)-phosphine complexes of carbazolate, [Au(PR3)(cbz)] (R = Me, Et, Cy, Ph, C6H4F and C6H4CF3, cbz = carbazolate ), and the absorption spectra of [Au(PMe3)(cbz)] are obtained by utilizing ab initio potential energy surfaces.  The nature of the spectra and low-lying electronic excited state is studied with inclusion of relativistic and correlation effects.  The ground state (S0) and the first triplet state (T1) of the complexes are described at density functional B3LYP /LanL2DZ and multi-reference single and double excitation configuration interaction (MRDCI) level of theory; the B3LYP /LanL2DZ optimized geometries, harmonic frequencies, and the vibration normal modes are calculated.  Their low-lying excited states were investigated by time-dependent density functional theory (TD-DFT), single-excited configuration interactions (CIS), and MRDCI.  In addition, the optimized geometries, harmonic frequencies, and the normal modes of the S1 and S3 states for Au(PMe3)(cbz) were obtained by employing CIS/LanL2DZ calculations.  The vibronic bands of three electronic transitions, S0 � S3, S0 � S1, S0 � T1, are obtained to simulate the observed [Au(PMe3)(cbz)] absorption spectra, which indicate nature of mixed carbarzole � carbazole and carbazole � Au transitions.  The Franck-Condon factor simulated vibronic bands of T1 � S0 transition for all six complexes are computed to provide insight for the experimental phosphorescence spectra; those of [Au(PMe3)(cbz)] and [Au(PEt3)(cbz)] almost coincide with their phosphorescence spectra, and are found to be transition of carbazole to carbazole in character.

Franck-Condon simulated spectra of carbazolate containing gold(I)-phosphine complexes

243rd National Meeting (2012)

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