TY - JOUR
T1 - Molecular and electronic structure of cyclic trinuclear gold(I) Carbeniate complexes
T2 - Insights for structure/luminescence/conductivity relationships
AU - McDougald, Roy N.
AU - Chilukuri, Bhaskar
AU - Jia, Huiping
AU - Perez, Michael R.
AU - Rabaâ, Hassan
AU - Wang, Xiaoping
AU - Nesterov, Vladimir N.
AU - Cundari, Thomas R.
AU - Gnade, Bruce E.
AU - Omary, Mohammad A.
PY - 2014/7/21
Y1 - 2014/7/21
N2 - 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, nBu, or cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN=CO nBu)3], [Au3(nBuN=COMe) 3], [Au3(nBuN=COnBu)3], and [Au3(cPeN=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 [Au 3(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/cm2. Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.
AB - 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, nBu, or cPe), is reported. Synthesis and structural and photophysical characterization of novel complexes [Au3(MeN=CO nBu)3], [Au3(nBuN=COMe) 3], [Au3(nBuN=COnBu)3], and [Au3(cPeN=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 [Au 3(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/cm2. Computations and experiments thus delineate the complex relationships between solid-state morphologies, electronic structures, and optoelectronic properties of gold(I) carbeniates.
UR - http://www.scopus.com/inward/record.url?scp=84904652134&partnerID=8YFLogxK
U2 - 10.1021/ic500808q
DO - 10.1021/ic500808q
M3 - Article
AN - SCOPUS:84904652134
SN - 0020-1669
VL - 53
SP - 7485
EP - 7499
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 14
ER -