Inhomogeneous Quantized Single-Electron Charging and Electrochemical-Optical Insights on Transition-Sized Atomically Precise Gold Nanoclusters.

ABSTRACT

Small differences in electronic structures, such as an emerging energy band gaps or the splitting of degenerated orbitals, are very challenging to resolve but important for nanomaterials properties. A signature electrochemical property called quantized double layer charging, i.e., "continuous" one-electron transfers (1e, ETs), in atomically precise Au133(TBBT)52, Au144(BM)60, and Au279(TBBT)84 is analyzed to reveal the nonmetallic to metallic transitions (whereas TBBT is 4-tert-butylbenzenethiol and BM is benzyl mercaptan; abbreviated as Au133, Au144, and Au279). Subhundred milli-eV energy differences are resolved among the "often-approximated uniform" peak spacings from multipairs of reversible redox peaks in voltammetric analysis, with single ETs as internal standards for calibration and under temperature variations. Cyclic and differential pulse voltammetry experiments reveal a 0.15 eV energy gap for Au133 and a 0.17 eV gap for Au144 at 298 K. Au279 is confirmed metallic, displaying a "bulk-continuum" charging response without an energy gap. The energy gaps and double layer capacitances of Au133 and Au144 increase as the temperature decreases. The temperature dependences of charging energies and HOMO-LUMO gaps of Au133 and Au144 are attributed to the counterion permeation and the steric hindrance of ligand, as well as their molecular compositions. With the subtle energy differences resolved, spectroelectrochemistry features of Au133 and Au144 are compared with ultrafast spectroscopy to demonstrate a generalizable analysis approach to correlate steady-state and transient energy diagram for the energy-in processes. Electrochemiluminescence (ECL), one of the energy-out processes after the charge transfer reactions, is reported for the three samples. The ECL intensity of Au279 is negligible, whereas the ECLs of Au133 and Au144 are relatively stronger and observable (but orders of magnitudes weaker than our recently reported bimetallic Au12Ag13). Results from these atomically precise nanoclusters also demonstrate that the combined voltammetric and spectroscopic analyses, together with temperature variations, are powerful tools to reveal subtle differences and gain insights otherwise inaccessible in other nanomaterials.