Predicting Excited-State and Luminescence Properties of a Cyclometalated Iridium(III) Complex: Quantum Mechanics/Molecular Mechanics Study

• Published in: Journal of physical chemistry. C Vol. 125; no. 10; pp. 5670 - 5677
• Main Authors: Gao, Yuan-Jun, Zhang, Ting-Ting, Chen, Wen-Kai
• Format: Journal Article
• Language: English
• Published: American Chemical Society 18.03.2021
• Subjects: C: Spectroscopy and Dynamics of Nano, Hybrid, and Low-Dimensional Materials
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.0c09464

The excited-state and luminescence properties of a cyclometalated Ir­(III) complex with two C∧N ligands (C∧N = 2-(2,4-difluorophenyl)­pyridine, F2ppy) and one acyclic diamino carbene (ADC) ancillary ligand have been investigated by employing computational chemistry methods. We also considered the environmental effects on excited-state properties in CH2Cl2 solution and crystal. The less overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) can reduce the energy gap ΔE ST between the lowest excited singlet and triplet states. The calculated fluorescence emission peak (S1 → S0) matches with the experimental values in two media. The small ΔE ST and proper spin–orbit coupling matrix elements (SOCMEs) facilitate the reverse intersystem crossing (rISC) processes from T1 to S1 states. Moreover, the forward ISC process takes precedence over transient fluorescence emission and reverse ISC process is also faster than the corresponding phosphorescence emission. This effect may be observed both in the dichloromethane solution and in crystal. By absorbing thermal energy, the excitons of T1 states upconvert to S1 states and then radiate energy from S1 states. As a consequence, this Ir complex displays typical characteristics of thermally activated delayed fluorescence (TADF) emitters, and it promises to be the first example of Ir complex with TADF.