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>i.e.</i>, "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-<i>tert</i>-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.