Photochemical Disproportionation of an AuII Pincer Complex: Synthesis and Structure of an Au4IAu4III Macrocycle

The Au(II) (CNC)-N-boolean AND-C-boolean AND pincer complex [((CNC)-N-boolean AND-C-boolean AND)Au](2) is stable under thermal conditions but disproportionates on irradiation in solution to give an Au(I)(4)Au(III)(4) mixed-valence aggregate with a 20-membered macrocyclic structure, consisting of four linear Au(I) C-Au-N building blocks, each of which is decorated with a square planar ((CNC)-N-boolean AND-C-boolean AND)Au(III) substituent. In the crystal, the rings are stacked to form solvent-filled channels with an internal diameter of 8.3 angstrom and a cross-channel Au-I center dot center dot center dot Au-I distance of 7.7 angstrom.