Orthogonal quintuple-stimuli responsiveness in an ultrastable, ultrabright Cu₁₆ nanocluster via molecular and supramolecular engineering

Abstract

The development of high-performance, universal stimuli-responsive materials is hindered by the disconnect between fundamental design principles and macroscopic multifunctionality. Herein, we report an atomically precise copper nanocluster Cu16, engineered with the dual alkynyl/perfluorocarboxylate ligands to simultaneously control molecular and supramolecular assembly. Endowed with ambient ultrastability and ultrabright luminescence, Cu16 undergoes well-defined, stimuli-induced changes that produce distinct, high-contrast responses to five functionally independent stimuli. Systematic studies reveal that Cu16 operates through a dual-channel responsive mechanism, where the structural channel governs responses to volatile organic compounds and pressure via structural perturbations at different extents, and the luminescent channel mediates responses to temperature, O2, and X-ray radiation via distinct electronic state transitions. The orthogonal discrimination of five stimuli yields quintuple optical switching effects, which not only establishes Cu16 as a state-of-the-art stimuli-responsive metal cluster with multidimensional signaling capability, but also confers unprecedented functional breadth. This work provides an atomic-precision blueprint to engineer advanced stimuli-responsive materials with multifunctionality, revealing explicit synthesis–structure–property correlations to guide the development of next-generation programmable smart materials.