QM/MM studies on luminescence mechanism of dinuclear copper iodide complexes with thermally activated delayed fluorescence

The QM/MM method is employed to investigate the photophysical mechanism of two dinuclear copper iodide complexes with thermally activated delayed fluorescence (TADF). The S(1)–T(1) energy differences (ΔE(ST)) in these two complexes are small enough so that repopulating the S(1) state from T(1) becomes energetically allowed. Both forward and reverse intersystem crossing (ISC and rISC) processes are much faster than the corresponding radiative fluorescence and phosphorescence processes [k(ISC) (10(8) s(−1)) > k(F)(r) (10(6) s(−1)), k(rISC) (10(5) s(−1)) > k(P)(r) (10(3) s(−1))]. The faster rISC process than the phosphorescence emission enables TADF. Moreover, the diphosphine ligands are found to play an important role in regulating the electronic structures and thereto the radiative and nonradiative rate constants. The present work rationalizes experimental phenomena and helps understand the intrinsic luminescence properties. The obtained insights could be useful for tuning the luminescence performance of dicopper-based luminescence materials.