Molecular and Electronic Structure of Cyclic Trinuclear Gold(I) Carbeniate Complexes: Insights for Structure/Luminescence/Conductivity Relationships
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- 作者：Roy N. McDougald ; Jr. ; Bhaskar Chilukuri ; Huiping Jia ; Michael R. Perez ; Hassan Raba芒 ; Xiaoping Wang ; Vladimir N. Nesterov ; Thomas R. Cundari ; Bruce E. Gnade ; Mohammad A. Omary
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：July 21, 2014
- 年：2014
- 卷：53
- 期：14
- 页码：7485-7499
- 全文大小：673K
- ISSN：1520-510X
文摘
An experimental and computational study of correlations between solid-state structure and optical/electronic properties of cyclotrimeric gold(I) carbeniates, [Au3(RN鈺怌OR鈥?3] (R, R鈥?= H, Me, nBu, or cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN鈺怌OnBu)3], [Au3(nBuN鈺怌OMe)3], [Au3(nBuN鈺怌OnBu)3], and [Au3(cPeN鈺怌OMe)3] are presented. Changes in R and R鈥?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鈺怌OR鈥?3] was investigated via molecular and solid-state simulations. Calculations on [Au3(HN鈺怌OH)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 (位). 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鈥攄oped within a poly(9-vinylcarbazole) host鈥攑roduced a colossal increase in current density from 1 to 1000 mA/cm2. Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.