Carborane-thiol protected copper nanoclusters: stimuli-responsive materials with tunable phosphorescence

Abstract

Atomically precise nanomaterials with tunable solid-state luminescence attract global interest. In this work, we present a new class of thermally stable isostructural tetranuclear copper nanoclusters (NCs), shortly Cu₄@oCBT, Cu₄@mCBT and Cu₄@ICBT, protected by nearly isomeric carborane thiols: <i>ortho</i>-carborane-9-thiol, <i>meta</i>-carborane-9-thiol and <i>ortho</i>-carborane 12-iodo 9-thiol, respectively. They have a square planar Cu₄ core and a butterfly-shaped Cu₄S₄ staple, which is appended with four respective carboranes. For Cu₄@ICBT, strain generated by the bulky iodine substituents on the carboranes makes the Cu₄S₄ staple flatter in comparison to other clusters. High-resolution electrospray ionization mass spectrometry (HR ESI-MS) and collision energy-dependent fragmentation, along with other spectroscopic and microscopic studies, confirm their molecular structure. Although none of these clusters show any visible luminescence in solution, bright μs-long phosphorescence is observed in their crystalline forms. The Cu₄@oCBT and Cu₄@mCBT NCs are green emitting with quantum yields (<i>Φ</i>) of 81 and 59%, respectively, whereas Cu₄@ICBT is orange emitting with a <i>Φ</i> of 18%. Density functional theory (DFT) calculations reveal the nature of their respective electronic transitions. The green luminescence of Cu₄@oCBT and Cu₄@mCBT clusters gets shifted to yellow after mechanical grinding, but it is regenerated after exposure to solvent vapour, whereas the orange emission of Cu₄@ICBT is not affected by mechanical grinding. Structurally flattened Cu₄@ICBT didn't show mechanoresponsive luminescence in contrast to other clusters, having bent Cu₄S₄ structures. Cu₄@oCBT and Cu₄@mCBT are thermally stable up to 400 °C. Cu₄@oCBT retained green emission even upon heating to 200 °C under ambient conditions, while Cu₄@mCBT changed from green to yellow in the same window. This is the first report on structurally flexible carborane thiol appended Cu₄ NCs having stimuli-responsive tunable solid-state phosphorescence.