Yersin, Hartmut and Czerwieniec, Rafal and Monkowius, Uwe and Ramazanov, Ruslan and Valiev, Rashid and Shafikov, Marsel Z. and Kwok, Wai-Ming and Ma, Chensheng (2023) Intersystem crossing, phosphorescence, and spin-orbit coupling. Two contrasting Cu(I)-TADF dimers investigated by milli- to micro-second phosphorescence, femto-second fluorescence, and theoretical calculations. COORDINATION CHEMISTRY REVIEWS, 478: 214975. ISSN 0010-8545, 1873-3840
Full text not available from this repository. (Request a copy)Abstract
Applying femto-second time-resolved spectroscopy, we study intersystem crossing times iota(ISC) of two Cu(I) dimers, Cu2Cl2(dppb)(2) 1 (dppb = 1,2-bis-diphenylphosphino)benzene) and Cu2Cl2((NP)-P-boolean AND)(2) 2 ((NP)-P-boolean AND = 2-(diphenylphosphino)-6-methylpyridine) used as powders. '(ISC) varies by more than one order of mag-nitude from 39 ps (1) to 3.7 ps (2). A similar trend is displayed in the radiative phosphorescence decay time iota(r)(T1) and the zero-field splitting (ZFS) amounting to iota(r)(T-1) = 4.2 ms and ZFS < 1 cm(-1) (0.1 meV) for 1 and 45 ls and 15 cm(-1) (1.9 meV) for 2. Simple quantum mechanical considerations and TD-DFT cal-culations allow us to correlate these different photophysical mechanisms. This is related to the efficiency of spin-orbit coupling (SOC), in particular with respect to the triplet state T-1. Presumably, inter-metallic interactions, occurring in 2, are the source of the much more efficient SOC between T-1 and neighboring states, thus, providing a relation between structure and photophysical properties. Accordingly, easily accessible phosphorescence data or even just structure data might already help to predict trends in ISC, at least for Cu(I) dimers. As for TADF emitters applied in OLEDs, iota(ISC) should be as fast as possible, the presented discussions might help to better understand ISC processes, in particular, with respect of speeding them up. (c) 2022 Elsevier B.V. All rights reserved.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ACTIVATED DELAYED FLUORESCENCE; LIGHT-EMITTING-DIODES; PHOTOINDUCED STRUCTURAL-CHANGE; CHARGE-TRANSFER STATES; COPPER(I) COMPLEXES; EXCITED-STATE; TRIPLET EMITTERS; PHOTOPHYSICAL PROPERTIES; OSMIUM(II) COMPLEXES; TRANSIENT ABSORPTION; Thermally activated delayed fluorescence; (TADF); Intersystem crossing; Fluorescence; Phosphorescence; Copper(I) dimers; Spin-orbit coupling; Femtosecond spectroscopy; Organic light emitting diodes (OLEDs) |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry) > Prof. Dr. Hartmut Yersin |
| Depositing User: | Petra Gürster |
| Date Deposited: | 02 Feb 2024 06:28 |
| Last Modified: | 02 Feb 2024 06:28 |
| URI: | https://pred.uni-regensburg.de/id/eprint/57927 |
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