Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Excimers and exciplexes are defined as assemblies of atoms or molecules A/A′ where interatomic/intermolecular bonding appears only in excited states such as [A (2)]* (for excimers) and [AA′]* (for exciplexes). Their formation has become widely known because of their role in gas‐phase laser technologies, but their significance in general chemistry terms has been given little attention. Recent investigations in gold chemistry have opened up a new field of excimer and exciplex chemistry that relies largely on the preorganization of gold(I) compounds (electronic configuration Au(I)(5d(10))) through aurophilic contacts. In the corresponding excimers, a new type of Au⋅⋅⋅Au bonding arises, with bond energies and lengths approaching those of ground‐state Au−Au bonds between metal atoms in the Au(0)(5d(10)6s(1)) and Au(II)(5d(9)) configurations. Excimer formation gives rise to a broad range of photophysical effects, for which some of the relaxation dynamics have recently been clarified. Excimers have also been shown to play an important role in photoredox binuclear gold catalysis.