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

Abstract

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 ∼10 3 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.

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

“…Section 3.1.2). DFT has been used to investigate piezochromism in Ir(III), 252,253 Ni(II), 254 and Cu(I) 255 complexes. In the latter case, energy decomposition analysis (EDA) 256 allowed the quantification of important energetic factors, for example, Pauli repulsion, electrostatic interactions, and dispersion, each of which shows complex and system-specific pressure-dependence.…”

Computational High-Pressure Chemistry: Ab Initio Simulations of Atoms, Molecules and Extended Materials in the Gigapascal Regime

“…Section 3.1.2). DFT has been used to investigate piezochromism in Ir(III), [243,244] Ni(II) [245] and Cu(I) [246] complexes. In the latter case, Energy Decomposition Analysis (EDA) [247] al-lowed the quantification of important energetic factors, e.g., Pauli repulsion, electrostatic interactions and dispersion, each of which shows complex and system-specific pressure-dependence.…”