Molecular and Electronic Structure of Cyclic Trinuclear Gold(I) Carbeniate Complexes: Insights for Structure/Luminescence/Conductivity Relationships

Autor: Bhaskar Chilukuri, Michael R. Perez, Xiaoping Wang, Thomas R. Cundari, Huiping Jia, Vladimir N. Nesterov, Bruce E. Gnade, Hassan Rabaâ, Mohammad A. Omary, Roy N. McDougald
Rok vydání: 2014
Předmět:
Zdroj: Inorganic Chemistry. 53:7485-7499
ISSN: 1520-510X
0020-1669
DOI: 10.1021/ic500808q
Popis: 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.
Databáze: OpenAIRE
Externí odkaz: