Near-Infrared Dual-Emission of a Thiolate-Protected Au 42 Nanocluster: Excited States, Nonradiative Rates, and Mechanism.

Both DFT and TD-DFT methods are used to elaborate on the excited-state properties and dual-emission mechanism of a thiolate-protected Au42 nanocluster. A three-state model (S, S, and T) is proposed with respect to the results. The intersystem crossing (ISC) process from S to T benefits from a small reorganization energy due to the similar geometric structures of S and T. However, the ISC process is suppressed by relatively small spin-orbit coupling resulting from the similarity of the electronic structures of S and T. As a result of the counterbalance, the ISC rate is comparable with the fluorescence emission rate. In the T state, the phosphorescence emission prevails the reverse ISC process back to the S state. Taken together, fluorescence and phosphorescence are achieved simultaneously. The present work provides deep mechanistic insights to aid the rational design of NIR dual-emissive metal nanoclusters.