1 research outputs found
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
goldÂ(I) carbeniates, [Au<sub>3</sub>(RNî—»COR′)<sub>3</sub>] (R, R′ = H, Me, <sup>n</sup>Bu, or <sup>c</sup>Pe), is reported.
Synthesis and structural and photophysical characterization of novel
complexes [Au<sub>3</sub>(MeNî—»CO<sup>n</sup>Bu)<sub>3</sub>], [Au<sub>3</sub>(<sup>n</sup>BuNî—»COMe)<sub>3</sub>], [Au<sub>3</sub>(<sup>n</sup>BuNî—»CO<sup>n</sup>Bu)<sub>3</sub>], and
[Au<sub>3</sub>(<sup>c</sup>PeNî—»COMe)<sub>3</sub>] 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<sub>3</sub>(RNCOR′)<sub>3</sub>] was
investigated via molecular and solid-state simulations. Calculations
on [Au<sub>3</sub>(HNî—»COH)<sub>3</sub>] 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 cyclotrimerî—¸doped
within a polyÂ(9-vinylcarbazole) hostî—¸produced a colossal increase
in current density from ∼1 to ∼1000 mA/cm<sup>2</sup>. Computations and experiments thus delineate the complex relationships
between solid-state morphologies, electronic structures, and optoelectronic
properties of goldÂ(I) carbeniates