title: Molecular and electronic structure of cyclic trinuclear gold(I) carbeniate complexes: insights for structure/luminescence/conductivity relationships.
abstract: 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.
authors: Department of Chemistry, Center for Advanced Research and Technology (CART) and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas , Denton, Texas 76203, United States.
authors: Roy N
authors: RN
authors: McDougald
authors: Bhaskar
authors: B
authors: Chilukuri
authors: Huiping
authors: H
authors: Jia
authors: Michael R
authors: MR
authors: Perez
authors: Hassan
authors: H
authors: Rabaâ
authors: Xiaoping
authors: X
authors: Wang
authors: Vladimir N
authors: VN
authors: Nesterov
authors: Thomas R
authors: TR
authors: Cundari
authors: Bruce E
authors: BE
authors: Gnade
authors: Mohammad A
authors: MA
authors: Omary