Abstract
The ground- and excited-state structures were fully optimized for a series of neutral binuclear Au(I) thiolates, [Au2(dpm)(SCH2S)] (1) (dpm=bis(diphosphino)methane), trans-[Au2(PH2CH2S)2] (2), and trans-[Au2(SHCH2S)2] (3), by using the MP2 and CIS methods, respectively. The calculated AuI–AuI distances of about 3.0 Å in the ground state of the complexes are indicative of aurophilic attraction between the two Au(I) atoms, while in their excited states the separations are greatly shortened (about 2.7–2.9 Å). The promotion of Au d electron or S p electron into the bonding sσ and/or pσ lowest unoccupied molecular orbital of AuI–AuI results in such reinforcement of aurophilicity in the excited state. In the CIS calculations of the three Au(I) thiolates, we obtained the lowest-energy phosphorescent emission in the solid state for each of the complexes. The 462 nm emission of 1 was assigned as Au→S charge transfer (MLCT) transition. But for 3, the charge transfer localized on the Au centers, Au3(sσ)→1Au(dσ*) (metal-centered charge transfer, MCCT), plays a main role in the 413 nm emission. Both the MCCT and MLCT transitions are important in the 323 nm emission of 2. The results indicated that AuI–AuI aurophilicity clearly influences luminescent properties of these complexes.
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