Reversible Mechanochromic Luminescence of Tetranuclear Cuprous Complexes

Mechanochromic luminescence materials have attracted rapidly growing interest. Nevertheless, the designed synthesis of such materials remains a challenge, and there have been few examples based on weak intramolecular interactions. Herein, we report a new approach for preparing mechanochromic luminescence materials of Cu(I) complexes, i.e., constructing a photoluminescence system that bears a large coplanar multinuclear Cu(I) unit showing weak intramolecular π···π interactions with the planar rings of the coordinated ligands in the molecule. Using it, a series of novel mechanochromic luminescent tetranuclear Cu(I) complexes have been successfully designed and synthesized. As revealed by single-crystal X-ray crystallography, these Cu(I) complexes share an identical {Cu₄[μ₃-η²(N,N),η¹(N),η¹(N)-pyridyltetrazole]₂}²⁺ planar fragment whose coplanar pyridyl rings exhibit weak intramolecular π···π interactions with the phenyl rings of the coordinated phosphine ligands in the molecule. All of these Cu(I) complexes exhibit reversible mechanochromic luminescence, which can be attributed to the change in the rigidity of the molecular structure resulting from the disruption and restoration of intramolecular π···π interactions between the pyridyl and phenyl rings triggered by grinding and CH₂Cl₂ vapor, as supported by powder X-ray diffraction and Fourier transform infrared spectrometry. In addition, the results might provide a new route for developing mechanochromic luminescence materials of Cu(I) complexes for intelligent responsive luminescent devices.