Ligand Detachment—New Insight into the Mechanochromic Luminescence Mechanism of Copper Iodide Complexes with Thermally Activated Delayed Fluorescence

Abstract Mechanochromic luminescence materials have recently attracted increasing interest due to its promising applications, but the intensive inquiry of the mechanochromic luminescence mechanism is still insufficient. Herein, an in‐depth study of mechanochromic luminescent copper iodide complexes exhibiting ligand detachment and structural transformation is reported. The yellowish–green emissive CuI(dmpz) (dmpz = 2,6‐dimethylpyrazine) is ground into orange–red emissive CuI(dmpz)_0.5 and the detailed structural transformation process is revealed by the thorough analysis of the crystalline structure before and after grinding. More importantly, new insight into the mechanochromic luminescence mechanism is proposed, that is, under the external force of grinding, the dmpz ligand detachment triggers the structural transformation from 1D chain to 2D network, which leads to the reduction of band gap energy and contraction of Cu─Cu bonds, together resulting in the red shift of luminescence ultimately. Moreover, the two complexes are also found to have thermochromic luminescence properties, attributing to their thermally activated delayed fluorescence process. The anti‐counterfeiting application of CuI(dmpz) is tentatively explored, demonstrating the favorable application prospect of CuI(dmpz). This study provides new insights involved in the mechanochromic luminescence mechanism of copper iodide complexes, and may provide a new understanding for rational molecular design and structural regulation of intelligent responsive luminescence.