Molecular and electronic structure of cyclic trinuclear gold(I) carbeniate complexes: insights for structure/luminescence/conductivity relationships.

An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au3(RN═COR')3] (R, R' = H, Me, (n)Bu, or (c)Pe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN═CO(n)Bu)3], [Au3((n)BuN═COMe)3], [Au3((n)BuN═CO(n)Bu)3], and [Au3((c)PeN═COMe)3] are presented. Changes in R and R' lead to distinctive variations in solid-state stacking, luminescence spectra, and conductive properties. Solid-state emission and excitation spectra for each complex display a remarkable dependence on the solid-state packing of the cyclotrimers. The electronic structure of [Au3(RN═COR')3] was investigated via molecular and solid-state simulations. Calculations on [Au3(HN═COH)3] models indicate that the infinitely extended chain of eclipsed structures with equidistant Au--Au intertrimer aurophilic bonding can have lower band gaps, smaller Stokes shifts, and reduced reorganization energies (λ). The action of one cyclotrimer as a molecular nanowire is demonstrated via fabrication of an organic field effect transistor and shown to produce a p-type field effect. Hole transport for the same cyclotrimer-doped within a poly(9-vinylcarbazole) host-produced a colossal increase in current density from ∼1 to ∼1000 mA/cm(2). Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.