Eight‐Electron Copper Nanoclusters for Photothermal Conversion

Owing to distinct physicochemical properties in comparison to gold and silver counterparts, atomically precise copper nanoclusters are attracting embryonic interest in material science. The introduction of copper cluster nanomaterials in more interesting fields is currently urgent and desired. Reported in this work are novel copper nanoclusters of [XCu54Cl12(tBuS)20(NO3)12] (X=S or none, tBuSH=2‐methyl‐2‐propanethiol), which exhibit high performance in photothermal conversion. The clusters have been prepared in one pot and characterized by combinatorial techniques including ultraviolet‐visible spectroscopy (UV‐vis), electrospray ionization mass spectrometry (ESI‐MS), and X‐ray photoelectron spectroscopy (XPS). The molecular structure of the clusters, as revealed by single crystal X‐ray diffraction analysis (SCXRD), shows the concentric three‐shell Russian doll arrangement of X@Cu14@Cl12@Cu40. Interestingly, the [SCu54Cl12(tBuS)20(NO3)12] cluster contains 8 free valence electrons in its structure, making it the first eight‐electron copper nanocluster stabilized by thiolates. More impressively, the clusters possess an effective photothermal conversion (temperature increases by 71 °C within ~50 s, λex=445 nm, 0.5 W cm−2) in a wide wavelength range (either blue or near‐infrared). The photothermal conversion can be even driven under irradiation of simulated sunlight (3 sun), endowing the clusters with great potency in solar energy utilization. Atomically precise Cu54 nanoclusters with eight free valence electrons have been prepared, characterized, and structurally determined. The clusters show high performance in the field of photothermal conversion. For the first time, atomically precise copper nanoclusters are proved to be effective in photothermal application, which may stimulate the research on using copper nanoclusters in material sciences.