Fabrication of Highly-Efficient Thermally Activated Delayed Fluorescence-Type Organic Afterglow Materials Based on Intramolecular Charge Transfer Technology

doi:10.6023/cjoc202503027

Abstract

The construction of highly efficient visible-light-excitable afterglow materials based on thermally activated delayed fluorescence (TADF) mechanism is reported, employing an intramolecular charge transfer technology. The resulting TADF- type afterglow materials exhibit emission lifetimes in the range of hundreds of milliseconds and photoluminescence quantum yields of approximately 50%, demonstrating remarkable temperature-responsive properties. By introducing additional electron- donating groups into the donor-acceptor (D-A)-type difluoroboron β-diketonate (BF₂bdk) molecules, donor-acceptor-donor (D-A-D)-type compounds were designed. These compounds exhibit a moderate rate of reverse intersystem crossing (RISC), thereby promoting the emergence of TADF-type afterglow within a rigid crystalline matrix. Furthermore, the D-A-D design approach elevates the highest occupied molecular orbital (HOMO) energy level, enabling TADF-type afterglow emission under visible light excitation. The research findings highlight the significance of intramolecular charge transfer technology in advancing the design of high-performance organic TADF-type afterglow materials.

Key words: difluoroboron β-diketonate, thermally activated delayed fluorescence, organic afterglow, room-temperature phos- phorescence, intramolecular charge transfer

Cite this article

Ting Luo, Yufeng Xiao, Xun Li, Wen Xia, Kaka Zhang. Fabrication of Highly-Efficient Thermally Activated Delayed Fluorescence-Type Organic Afterglow Materials Based on Intramolecular Charge Transfer Technology[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4202-4209.

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Fig. & Tab. 5

Figure 1. (a) BF2bdk compound; (b) Synthesis method of D-A-D type BF2bdk compound; (c) Chemical structures of the BF2bdk compounds used in this study

Figure 2. (a~c) Room temperature steady-state and delayed emission (1 ms delay) spectra of 1-MeOBP with doping concentrations of 0.001%, 0.01%, 0.1% excited at 365 nm and photographs of the material under 365 nm UV lamp and after removing the UV lamp; (d~f) Room temperature emission decay curves of 1-MeOBP with doping concentrations of 0.001%, 0.01%, 0.1%

Figure 3. (a) Delay emission spectra (1 ms delay) of 1-MeOBP-0.001% at different temperatures; (b) Emission decay curves of 1-MeOBP-0.001% at different temperatures monitored at 470 nm; (c) Fitted line plot of 1-MeOBP-0.001% ln(kRISC) and 1/T with slope associated with △EST; (d) Schematic illustration of TADF-type organic afterglow mechanism in BF2bdk-MeOBP system

Figure 4. Iso-surface map of electron hole density difference, excitation energy, oscillator strength and SOCME value for the singlet and triplet excited states of compound 1

Entry	λ_F/nm	λ_AG/nm	τ_AG/ms	PLQY/%
1-MeOBP-0.001%	470	470	211	55.1
2-MeOBP-0.001%	470	470	182	52.9
3-MeOBP-0.001%	470	470	248	47.8
4-MeOBP-0.001%	480	480	161	50.3

Table 1. Photophysical properties of afterglow materials

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