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. 2019 Nov 25;11(3):833-838.
doi: 10.1039/c9sc04632a.

Persistent organic room temperature phosphorescence: what is the role of molecular dimers?

Yunsheng Wang  1 , Jie Yang  1 , Yu Tian  1 , Manman Fang  1 , Qiuyan Liao  2 , Liwei Wang  1 , Wenping Hu  1 , Ben Zhong Tang  1   3 , Zhen Li  1   2   4
Affiliations

Persistent organic room temperature phosphorescence: what is the role of molecular dimers?

Yunsheng Wang et al. Chem Sci. .

Abstract

Molecular dimers have been frequently found to play an important role in room temperature phosphorescence (RTP), but its inherent working mechanism has remained unclear. Herein a series of unique characteristics, including singlet excimer emission and thermally activated delayed fluorescence, were successfully integrated into a new RTP luminogen of CS-2COOCH3 to clearly reveal the excited-state process of RTP and the special role of molecular dimers in persistent RTP emission.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. (A) The query about the role of dimers in the persistent RTP effect and the proposed solution, in which F1 indicates monomer-dominated fluorescence, P1 indicates monomer-dominated RTP, F2 indicates singlet excimer fluorescence and P2 indicates possible triplet excimer RTP. (B) The molecular structure and design strategy of CS-2COOCH3.
Fig. 2
Fig. 2. (A) The normalized steady-state PL spectra of CS-2COOCH3 in different states—crystal, ground state and doped in poly(methyl methacrylate) (PMMA) film in air. (B) The fluorescence decay curves of CS-2COOCH3 crystal at 405 and 505 nm in air. (C) The RTP spectra, acquired after 10 ms delay, of CS-2COOCH3 in different states—crystal, ground state and doped in PMMA film under air atmosphere. (D) The RTP decay curves of CS-2COOCH3 crystal at 430, 460 and 490 nm. Insets: photos of CS-2COOCH3 crystal before and after turning off 365 nm UV radiation in air.
Fig. 3
Fig. 3. Normalized PL spectra of CS-2COOCH3 crystal from 77 K to 298 K.
Fig. 4
Fig. 4. (A) The single-crystal structure and molecular dimer (side view and top view) of CS-2COOCH3. (B) The natural transition orbitals (NTOs) of the T1 state for the monomer and dimer of CS-2COOCH3.
Fig. 5
Fig. 5. Changing tendency of the fluorescent radiative rate (kr) and non-radiative rate (knr) for CS-2COOCH3 in different states.
Fig. 6
Fig. 6. The proposed PL process of CS-2COOCH3.
See this image and copyright information in PMC

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