Modulating the Extent of Anisotropic Cuprophilicity via High Pressure with Piezochromic Luminescence Sensitization

Metallophilicity has been widely studied as a fundamental supramolecular interaction. However, the extent and directionality thereof remain controversial. A major obstacle lies in the difficulty to separately control the geometry and chemical composition. Herein, we address this challenge by modulating metallophilicity with mechanical pressure. Using a multinuclear Cu(I) complex as model system, we report anomalous anisotropies of (supra)molecular structures, vibrations, and interaction energies upon isotropic compression as well as concomitant (essentially turn-on) piezochromic luminescence enhancement with similar to 103 modulation. The in situ characterizations indicate opposite behaviors of contact distances and cuprophilic interactions for intermolecular vs intramolecular Cu-Cu pairs under pressure. Theoretical calculations break down the attractive and repulsive forces associated with cuprophilicity, its spontaneous 4p-3d hybridization origin, and direction-dependent interaction strength. The use of isotropic mechanical force reveals the intrinsic anisotropy of metallophilicity in multinuclear systems.

Automated summary

Metallophilicity in multinuclear systems exhibits intrinsic anisotropy under isotropic compression, resulting in anomalous anisotropies in (supra)molecular structures, vibrations, and interaction energies. Mechanical pressure modulation also enhances piezochromic luminescence with similar to 103 modulation.