The luminescence properties of polynuclear transition metal complexes with a d 10 closed-shell electronic configuration have attracted much attention over the past few decades. [1] In view of the wide applicability of d 10 transition metal chalcogenides in semiconducting materials, photovoltaics, and nanomaterials, and their intriguing optical behavior, their spectroscopic and photophysical properties are worthy of exploration. With our recent success in making soluble polynuclear copper(i), silver(i), gold(i), zinc(ii), cadmium(ii) and mercury(ii) complexes with unsubstituted chalcogenide and chalcogenolate ligands and rich luminescence behavior, [2] we hope that, by systematic variation of the metal, chalcogen, and ancillary ligands, insights into the spectroscopic properties, the nature of the excited states, and the structure ± property relationship can be obtained. This is particularly important, as many of the transition metal chalcogenides and chalcogenolates are insoluble, and this renders their structures and photophysical properties less amenable to study. Owing to the recent growing interest in the aurophilic nature of gold(i) centers and the scantiness of gold(i) chalcogenide aggregates, [3±5] we launched a program to investigate this class of compounds. A number of soluble dodecanuclear and decanuclear gold(i) sulfido complexes with bridging diphosphane ligands have been successfully synthesized by us. [2c,d] These complexes have the formulas [Au 12 (m-dppm) 6 (m 3 -S) 4 ](PF 6 ) 4 (dppm bis(diphenylphosphanyl)methane) and [Au 10 {m-Ph 2 PN(nPr)PPh 2 } 4 (m 3 -S) 4 ](PF 6 ) 2 and possess novel structures and interesting photophysical behaviors. Here we report an unprecedented hexanuclear gold(i) sulfido complex with bridging diphosphane ligands, namely, 1, which has unusual photophysical properties.[Au 6 {m-Ph 2 PN(p-CH 3 C 6 H 4 )PPh 2 } 3 (m 3 -S) 2 ](ClO 4 ) 2 1Reaction of H 2 S with a suspension of [Au 2 {Ph 2 PN(p-CH 3 C 6 H 4 )PPh 2 }Cl 2 ] in ethanol/pyridine followed by metathesis reaction with LiClO 4 and recrystallization from acetone/dichloromethane/diethyl ether yielded 1 as colorless crystals in 50 % yield. It was characterized by elemental analysis, positive-ion FAB mass spectrometry, positive-and negative-ion ESI mass spectrometry, and 1 H and 31 P NMR spectroscopy. [6] The structure of the complex cation of 1 in the solid state was determined by X-ray crystallography. [7] The cation is hexanuclear, and the Au 6 S 2 unit is arranged in a distorted heterocubane structure with the two sulfur atoms at opposite apices of the cuboid. Figure 1 shows a perspective drawing of Figure 1. Perspective drawing of the structure of the complex cation of 1 in the crystal. Only the ipso-C atoms of the aromatic rings are shown for clarity. Thermal ellipsoids are drawn at the 30 % probability level. the cation. Each sulfur atom is bonded to three gold(i) centers in a m 3 bridging mode, and the two Au 3 S units are interconnected by three diphosphanylamin ligands. Noticeable gold ± gold interactions ar...
