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2022/03,祝贺赵静怡作为共同作者在Dalton Trans.上发表文章!
发布时间:2022-04-28

[5]Helicene-based chiral triarylboranes with large luminescence dissymmetry factors over a 10-2 level: synthesis and design strategy via isomeric tuning of steric substitutions

Constructing chiral luminescent systems with both large luminescence dissymmetry factor (glum) and high luminous efficiency has been considered a great challenge. We herein describe a highly efficient approach to sterically stabilize the helical configurations of carbo[5]helicenes for improved CPL properties in a series of π-donor and π-acceptor substituted [5]helicenes (1234 and 5). Enabled by the ortho-installation of methyl groups as well as the steric effects of triarylamine (Ar3N) and triarylborane (Ar3B) handles in meta-substituted [5]helicenes, their optical resolution into enantiomers has been accomplished using preparative chiral HPLC. The molecular chirality of [5]helicenes can be transferred to Ar3B and Ar3N as light emitters, which allowed further investigations of their chiroptics, including optical rotation, circular dichroism (CD) and circularly polarized luminescence (CPL). Remarkably, 4 has been demonstrated to display dramatically enhanced CPL performance with a much larger glum (>1.2 × 10−2) and an increased emission quantum efficiency (ΦS = 0.75) compared with the other analogues, as a result of the isomeric tuning of substitutions with differential steric and electronic effects. These experimentally observed CPL activities were rationalized by TD-DFT computations for the angle (θμ,m) between electric and magnetic transition dipole moments in the excited states. In addition, the conspicuous intramolecular donor–acceptor charge transfer led to thermal responses in the emissions of 2 and 4 over a broad temperature range.

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