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Abstract It is challenging to attain strong near-infrared (NIR) emissive gold nanoclusters. Here we show a rod-shaped cluster with the composition of [Au28(p-MBT)14(Hdppa)3](SO3CF3)2 (1 for short, Hdppa is N,N-bis(diphenylphosphino)amine, p-MBT is 4-methylbenzenethiolate) has been synthesized. Single crystal X-ray structural analysis reveals that it has a rod-like face-centered cubic (fcc) Au22 kernel built from two interpenetrating bicapped cuboctahedral Au15 units. 1 features NIR luminescence with an emission maximum at 920 nm, and the photoluminescence quantum yield (PLQY) is 12%, which is 30-fold of [Au21(m-MBT)12(Hdppa)2]SO3CF3 (2, m-MBT is 3-methylbenzenethiolate) with a similar composition and 60-fold of Au30S(S‑t‑Bu)18 with a similar structure. time-dependent DFT(TDDFT)calculations reveal that the luminescence of 1 is associated with the Au22 kernel. The small Stokes shift of 1 indicates that it has a very small excited state structural distortion, leading to high radiative decay rate (k r) probability. The emission of cluster 1 is a mixture of phosphorescence and thermally activated delayed fluorescence(TADF), and the enhancement of the NIR emission is mainly due to the promotion of k r rather than the inhibition of k nr. This work demonstrates that the metal kernel and the surface structure are both very important for cluster-based NIR luminescence materials.

Metal nanoclusters have emerged as promising near-infrared (NIR)–emissive materials, but their room-temperature photoluminescence quantum yield (PLQY), especially in solution, is often low (<10%). We studied the photophysics of Au22(tBuPhC≡C)18 (Au22) and its alloy counterpart Au16Cu6(tBuPhC≡C)18 (Au16Cu6) (where tBu is tert-butyl and Ph is phenyl) and found that copper (Cu) doping suppressed the nonradiative decay (~60-fold less) and promoted intersystem crossing rate (~300-fold higher). The Au16Cu6 nanocluster exhibited >99% PLQY in deaerated solution at room temperature with an emission maximum at 720 nanometers tailing to 950 nanometers and 61% PLQY in the oxygen-saturated solution. The approach to achieve near-unity PLQY could enable the development of highly emissive metal cluster materials. [ABSTRACT FROM AUTHOR]