Liu Dan-Yang, Li Hai-Yang, Han Run-Ping, Liu Hua-Li, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202307875. doi: 10.1002/anie.202307875. Epub 2023 Jul 27.
Stimuli-responsive circularly polarized luminescence (CPL) materials are ideal for information anti-countering applications, but the best-performing materials have not yet been identified. This work presents enantiomorphic hybrid antimony halides R-(C H NO) SbCl (1) and S-(C H NO) SbCl (2) showing mirror-imaged CPL activity with a dissymmetry factor of 1.2×10 . Interestingly, the DMF-induced structural transformation is realized to obtain non-emissive R-(C H NO) SbCl ⋅ DMF (3) and S-(C H NO) SbCl ⋅ DMF (4) upon exposure to DMF vapor. The transformation process is reversed upon heating. DFT calculations showed that the DMF-induced-quenched-luminescence is attributed to the intersection of the ground and excited state curves on the configuration coordinates. Unexpectedly, the nanocrystals of the chiral antimony halides 1 and 2 were prepared and indicate the excellent solution process performance. The reversible PL and CPL switching gives the system applications in information technology, anti-counterfeiting, encryption-decryption, and logic gates.
刺激响应型圆偏振发光(CPL)材料是信息防伪应用的理想选择,但尚未确定性能最佳的材料。这项工作展示了对映体杂化卤化锑R-(C₆H₅NO)SbCl₅(1)和S-(C₆H₅NO)SbCl₅(2),它们表现出镜像CPL活性,不对称因子为1.2×10⁻³。有趣的是,实现了DMF诱导的结构转变,在暴露于DMF蒸汽时得到非发光的R-(C₆H₅NO)SbCl₅·DMF(3)和S-(C₆H₅NO)SbCl₅·DMF(4)。加热时转变过程逆转。DFT计算表明,DMF诱导的发光猝灭归因于基态和激发态曲线在构型坐标上的交叉。出乎意料的是,制备了手性卤化锑1和2的纳米晶体,表明其具有优异的溶液加工性能。可逆的PL和CPL切换赋予该系统在信息技术、防伪、加密解密和逻辑门等方面的应用。