Tunable Photoinduced Charge Transfer at the Interface between Benzoselenadiazole-Based MOF Linkers and Thermally Activated Delayed Fluorescence Chromophore.
Shorooq A AlomarLuis Gutiérrez-ArzaluzIssatay NadinovRu HeXiaodan WangJian-Xin WangJiangtao JiaOsama ShekhahMohammed EddaoudiHusam N AlshareefKirk S SchanzeOmar F MohammedPublished in: The journal of physical chemistry. B (2023)
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.
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