A series of four electron-deficient-substituted Re(I) pyridyl N-heterocyclic carbene (pyNHC) complexes have been synthesized, and their electrocatalytic reduction of CO2 has been evaluated by cyclic voltammetry and controlled potential electrolysis experiments. All of the catalysts were evaluated by cyclic voltammetry under inert atmosphere and under CO2 and compared to the known benchmark catalyst Re(bpy)(CO)3Br. Among the four Re-NHC catalysts, Re(pyNHC-PhCF3)(CO)3Br (2) demonstrated the highest catalytic rate (icat/ip)(2) at the first and second reduction events with a value of 4 at the second reduction potential (TOF = 0.8 s(-1)). The rate of catalysis was enhanced through the addition of proton sources (PhOH, TFE, and H2O; TOF up to 100 s(-1); (icat/ip)(2) = 700). Controlled potential electrolysis shows Faradaic efficiencies (FE) for CO production and accumulated charge for the Re(pyNHC-PhCF3)(CO)3Br catalyst exceed those of the benchmark catalyst in the presence of 2 M H2O (92%, 13 C at 1 h versus 61%, 3 C for the benchmark catalyst) under analogous experimental conditions. A peak FE of 100% was observed during electrolysis with Re(pyNHC-PhCF3)(CO)3Br.

New methoxy substituted CNC pincers form ruthenium catalysts that are robust and convert CO2 to CO selectively using light energy.

Thieno[3,4-b]pyrazine (TPz) is examined as an electron deficient π-bridge enabling near-infrared (NIR) spectral access in dye-sensitized solar cells (DSCs). Seven dissymmetric dyes for DSCs were synthesized (NL2-NL8) with TPz as the π-bridge utilizing palladium catalyzed C-H activation methodology. C-H bond cross-coupling was uniquely effective among the cross-couplings and electrophilic aromatic substitution reactions analyzed in monofunctionalizing the TPz building block. The TPz-based NL2-NL8 dyes examine the effects of various donors, π-spacers, and acceptors within the donor-π bridge-acceptor (D-π-A) dye design. Proaromatic TPz stabilizes the excited-state oxidation potential (E(s+/s*)) of the dyes by maintaining aromaticity upon excitation of the dye molecule. This leads to concise conjugated systems capable of accessing the NIR region. Through judicious structural modifications, dye band gaps were reduced to 1.48 eV, and power conversion efficiencies (PCEs) reached 7.1% in this first generation TPz-dye series.

A series of thienopyrazine-based donor–acceptor–donor (D–A–D) near-infrared (NIR) fluorescent compounds were synthesized through a rapid, palladium-catalyzed C–H activation route. The dyes were studied through computational analysis, electrochemical properties analysis, and characterization of their photophysical properties. Large Stokes shifts of approximately 175 nm were observed, which led to near-infrared emission. Computational evaluation shows that the origin of this large Stokes shift is a significant molecular reorganization particularly about the D–A bond. The series exhibits quantum yields of up to φ = >4%, with emission maxima ranging from 725 to 820 nm. The emission is strong in solution, in thin films, and also in isolation at the single-molecule level. Their stable emission at the single-molecule level makes these compounds good candidates for single-molecule photon sources in the near-infrared.

The first example of a CNC pincer ligand with a central pyridinol ligand is reported in a nickel(ii) complex. This metal complex can be protonated or deprotonated reversibly in situ to switch on or off the photocatalytic performance towards CO2 reduction. The O- substituent appears essential for catalysis.