Open for Bismuth: Main Group Metal-to-Ligand Charge Transfer.

The synthesis, characterization, and photophysical properties of 4- and 6-coordinate Bi coordination complexes are reported. Bi(bzq) () and [Bi(bzq)]Br () (bzq = benzo[]quinoline) are synthesized by reaction of 9-Li-bzq with BiCl and BiBr, respectively. Absorption spectroscopy, electrochemistry, and DFT studies suggest that has 42% Bi 6s character in its highest-occupied molecular orbital (HOMO) as a result of six σ* interactions with the bzq ligands.

Binding Orientation of a Ruthenium-Based Water Oxidation Catalyst on a CdS QD Surface Revealed by NMR Spectroscopy.

We report on the binding of a Ru-based water oxidation catalyst (WOC) to CdS quantum dots (QDs) revealed by H NMR spectroscopy. Spin centers within the WOC exhibit correlated trends in chemical shift and lifetime shortening upon QD binding. These effects are a highly directional function of proton position within the WOC, thus uncovering orientation information relative to the QD surface.

Relationships between Exciton Dissociation and Slow Recombination within ZnSe/CdS and CdSe/CdS Dot-in-Rod Heterostructures.

Type-II and quasi type-II heterostructure nanocrystals are known to exhibit extended excited-state lifetimes compared to their single material counterparts because of reduced wave function overlap between the electron and hole. However, due to fast and efficient hole trapping and nonuniform morphologies, the photophysics of dot-in-rod heterostructures are more rich and complex than this simple picture. Using transient absorption spectroscopy, we observe that the behavior of electrons in the CdS "rod" or "bulb" regions of nonuniform ZnSe/CdS and CdSe/CdS dot-in-rods is similar regardless of the "dot" material, which supports previous work demonstrating that hole trapping and particle morphology drive electron dynamics.

Observation of trapped-hole diffusion on the surfaces of CdS nanorods.

In CdS nanocrystals, photoexcited holes rapidly become trapped at the particle surface. The dynamics of these trapped holes have profound consequences for the photophysics and photochemistry of these materials. Using a combination of transient absorption spectroscopy and theoretical modelling, we demonstrate that trapped holes in CdS nanorods are mobile and execute a random walk at room temperature.