Tunable Photoinduced Charge Transfer at the Interface between Benzoselenadiazole-Based MOF Linkers and Thermally Activated Delayed Fluorescence Chromophore

Abstract
Structural modifications to molecular systems that lead to the control of photon emission processes at the interfaces between photoactive materials play a key role in the development of fluorescence sensors, X-ray imaging scintillators, and organic light-emitting diodes (OLEDs). In this work, two donor–acceptor systems were used to explore and reveal the effects of slight changes in chemical structure on interfacial excited-state transfer processes. A thermally activated delayed fluorescence (TADF) molecule was chosen as the molecular acceptor. Meanwhile, two benzoselenadiazole-core MOF linker precursors, Ac-SDZ and SDZ, with the presence and absence of a C≡C bridge, respectively, were carefully chosen as energy and/or electron-donor moieties. We found that the SDZ -TADF donor–acceptor system exhibited efficient energy transfer, as evidenced by steady-state and time-resolved laser spectroscopy. Furthermore, our results demonstrated that the Ac-SDZ–TADF system exhibited both interfacial energy and electron transfer processes. Femtosecond-mid-IR (fs-mid-IR) transient absorption measurements revealed that the electron transfer process takes place on the picosecond timescale. Time-dependent density functional theory (TD-DFT) calculations confirmed that photoinduced electron transfer occurred in this system and demonstrated that it takes place from C≡C in Ac-SDZ to the central unit of the TADF molecule. This work provides a straightforward way to modulate and tune excited-state energy/charge transfer processes at donor–acceptor interfaces.

Citation
Alomar, S. A., Gutiérrez-Arzaluz, L., Nadinov, I., He, R., Wang, X., Wang, J.-X., Jia, J., Shekhah, O., Eddaoudi, M., Alshareef, H. N., Schanze, K. S., & Mohammed, O. F. (2023). Tunable Photoinduced Charge Transfer at the Interface between Benzoselenadiazole-Based MOF Linkers and Thermally Activated Delayed Fluorescence Chromophore. The Journal of Physical Chemistry B. https://doi.org/10.1021/acs.jpcb.2c08844

Acknowledgements
The authors thank King Abdullah University of Science and Technology (KAUST), the CARF-FCC/1/1972-63-01 project for financial support, and the Supercomputing Laboratory at KAUST for computational and storage resources.

Publisher
American Chemical Society (ACS)

Journal
The Journal of Physical Chemistry B

DOI
10.1021/acs.jpcb.2c08844

PubMed ID
36807993

Additional Links
https://pubs.acs.org/doi/10.1021/acs.jpcb.2c08844

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