Impact of Δ E ST on Delayed Fluorescence Rate, Lifetime, and Intensity Ratio of Tetrahedral Cu(I) Complexes: Theoretical Simulation in Solution and Solid Phases.

Autor: He TF; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Ren AM; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Li GH; Laboratory of Molecular Modeling and Design, State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, 457 Zhongshan Road, Dalian 116023, P.R. China., Qu ZX; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Guo JF; School of Physics, Northeast Normal University, Changchun 130024, P.R. China., Hao XL; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Chen YN; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Shen L; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Zhang YL; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China., Zou LY; Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P.R. China.
Jazyk: angličtina
Zdroj: The journal of physical chemistry letters [J Phys Chem Lett] 2021 Mar 11; Vol. 12 (9), pp. 2232-2244. Date of Electronic Publication: 2021 Feb 26.
DOI: 10.1021/acs.jpclett.1c00119
Abstrakt: Profound understanding of the luminescence mechanism and structure-property relationship is vital for Cu(I) thermally activated delayed fluorescence (TADF) emitters. Herein, we theoretically simulated luminescent behavior in both solution and solid phases for two Cu(I) complexes and found the following: (i) The strengthened spin-orbit coupling (SOC) effect by more d x 2 - y 2 orbital contributions and well-restricted structural distortion via remarkable intramolecular interaction in [Cu(dmp)(POP)] + enable the emission at room temperature to be a mixture of direct phosphorescence (10%) and TADF (90%). (ii) Benefiting from enhanced steric hindrance and the electron-donating ability of the paracyclophane group, the narrowed S 1 -T 1 energy separation (Δ E ST ) in [Cu(dmp)(phanephos)] + accelerates the reverse intersystem crossing, promoting the TADF rate (1.88 × 10 5 s -1 ) and intensity ratio (98.3%). These results indicate that the small Δ E ST is superior for reducing the lifetime and that the strong SOC stimulates the phosphorescence to compete with TADF, which are both conducive to avoiding collision-induced exciton quenching and reducing the roll-off in devices.
Databáze: MEDLINE
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