The modular construction of ligands around an N-heterocyclic carbene building block represents a flexible synthetic strategy for tuning the electronic properties of metal complexes. Herein, methylbenzimidazolium-pyridine and methylbenzimidazolium-pyrimidine proligands are constructed in high yield using recently established transition-metal-free techniques. Subsequent chelation to ReCl(CO)5 furnishes ReCl(N-methyl-N'-2-pyridylbenzimidazol-2-ylidine)(CO)3 and ReCl(N-methyl-N'-2-pyrimidylbenzimidazol-2-ylidine)(CO)3. These Re(I) NHC complexes are shown to be capable of mediating the two-electron conversion of CO2 following one-electron reduction; the Faradaic efficiency for CO formation is observed to be >60% with minor H2 and HCO2H production. Data from cyclic voltammetry is presented and compared to well-studied ReCl(2,2'-bipyridine)(CO)3 and MnBr(2,2'-bipyridine)(CO)3 systems. Results from density functional theory computations, infrared spectroelectrochemistry, and chemical reductions are also discussed.

The effect of disorder in the behavior of liquid crystal (LC) is assessed and controlled by dispersing known amounts of silica aerosil in the liquid crystal material. Using deuteron nuclear magnetic resonance, the director configuration and the orientational order was determined for hydrophilic aerosil dispersions in octylcyanobiphenyl. The confined liquid crystal exhibits a well-defined alignment as the silica spheres stabilize the molecular configuration. At low silica densities, a silica network is eventually established, forming a soft gel. When the sample orientation in the magnetic field is changed, a few silica strands links are broken and a fraction of the LC molecules is realigned. The field anneals the random disorder introduced by the aerosil up to a certain density beyond which, in the so-called stiff-gel regime, disordering effects completely dominate. At a fixed temperature in the isotropic phase, there is surface-induced order that is linearly proportional to the silica density.

Hybrid photocatalysts were prepared by depositing a macrocyclic cobalt complex on TiO2 surfaces. Upon UV light irradiation, photoexcited electrons in TiO2 nanoparticles were transferred to the surface cobalt catalyst for CO2 reduction.