Strong Solid-State Fluorescence Induced by Restriction of the Coordinate Bond Bending in Two-Coordinate Copper(I)–Carbene Complexes

The photophysical properties of two-coordinate copper(I) complexes have become a new research hotspot due to their nearly perfect luminescent properties and low price and promising applications in organic light-emitting diodes (OLEDs). In this work, we employ the hybrid quantum mechanics and molecular mechanics (QM/MM) approach, coupled with our early developed thermal vibration correlation function (TVCF) rate formalism, to study the aggregation effect on the luminescent properties of the cyclic (alkyl)(amino)carbene–copper(I)–Cl complex. Our calculations reveal that the transition properties changes from metal–ligand-charge-transfer (MLCT) in solution to hybrid halogen ligand charge-transfer (XLCT) and MLCT in solid state, which induces the blue-shifted emission spectra from solution to solid phase. Upon aggregation, the restriction of the bending vibrations of the C–Cu–Cl and Cu–C–N bonds largely slow down the nonradiative decay, which induces strong fluorescence. This study provides a clear rationaliz...