Chao Duobin, Zhao Mengying
School of Materials Science and Chemical Engineering, Ningbo University, Zhejiang 315211, China.
Dalton Trans. 2019 Apr 16;48(16):5444-5449. doi: 10.1039/c9dt00407f.
A noble-metal-free chromophore-catalyst supramolecular assembly, which is composed of an organic thermally activated delayed fluorescence (TADF) chromophore and cobaloximes, has been designed and synthesized for the first time for the efficient acceptorless dehydrogenation of secondary amines under blue light irradiation at room temperature. The TADF chromophore has a long lifetime of 17.4 μs with suitable redox potentials for the selective acceptorless dehydrogenation of secondary amines to afford imines and H2 through cooperative catalysis of the chromophore and cobaloximes in the supramolecular assembly. A high TON of 895 was obtained for the acceptorless dehydrogenation of 1,2,3,4-tetrahydroisoquinoline despite its high oxidation potential (+1.38 V vs. SCE).
首次设计并合成了一种无贵金属的发色团 - 催化剂超分子组装体，其由有机热活化延迟荧光（TADF）发色团和钴肟组成，用于在室温蓝光照射下高效地对仲胺进行无受体脱氢反应。该TADF发色团具有17.4 μs的长寿命，具有合适的氧化还原电位，可通过超分子组装体中发色团和钴肟的协同催化，将仲胺选择性地进行无受体脱氢反应生成亚胺和H2。尽管1,2,3,4 - 四氢异喹啉具有较高的氧化电位（相对于饱和甘汞电极，+1.38 V），但其无受体脱氢反应仍获得了高达895的高TON值。
