Synthesis and macrocyclization-induced emission enhancement of benzothiadiazole-based macrocycle.

Li, Shuo; Liu, Kun; Feng, Xue-Chen; Li, Zhao-Xian; Zhang, Zhi-Yuan; Wang, Bin; Li, Minjie; Bai, Yue-Ling et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

We presented an effective and universal strategy for the improvement of luminophore's solid-state emission, i.e., macrocyclization-induced emission enhancement (MIEE), by linking luminophores through C(sp<sup>3</sup>) bridges to give a macrocycle. Benzothiadiazole-based macrocycle (BT-LC) has been synthesized by a one-step condensation of the monomer 4,7-bis(2,4-dimethoxyphenyl)-2,1,3-benzothiadiazole (BT-M) with paraformaldehyde, catalyzed by Lewis acid. In comparison with the monomer, macrocycle BT-LC produces much more intense fluorescence in the solid state (Φ<sub>PL</sub> = 99%) and exhibits better device performance in the application of OLEDs. Single-crystal analysis and theoretical simulations reveal that the monomer can return to the ground state through a minimum energy crossing point (MECP<sub>S1/S0</sub>), resulting in the decrease of fluorescence efficiency. For the macrocycle, its inherent structural rigidity prohibits this non-radiative relaxation process and promotes the radiative relaxation, therefore emitting intense fluorescence. More significantly, MIEE strategy has good universality that several macrocycles with different luminophores also display emission improvement.