Hara Masaki, Toriumi Naoyuki, Uchiyama Masanobu, Nozaki Kyoko
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-8656, Japan.
Graduate School of Pharmaceutical Sciences, The, University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan.
Chemistry. 2024 Dec 13;30(70):e202402323. doi: 10.1002/chem.202402323. Epub 2024 Oct 31.
A one-pot procedure with cobalt-mediated oxidation of 2,2'-dilithio-1,1'-binaphthyl by ferrocenium salts afforded the chiral cyclic hexamer of naphthylene, [6]cyclo-1,2-naphthylene (1). The molecular structure of 1 was determined by single crystal X-ray crystallography and NMR analyses, revealing its cyclic structure with an approximate D symmetry. Compound 1 exhibits blue emission at 383 nm with high photoluminescence quantum yield of 97 %, which can be attributed to its rigid twelve-membered ring structure. Optical resolution of 1 by chiral HPLC allowed for the evaluation of its chiroptical properties. Each enantiomer exhibits circular dichroism with complex Cotton effects, which are grouped into three positive or three negative couplets. Circularly polarized luminescence is observed at 383 nm with an anisotropy factor |g| on the order of 10. The high photoluminescence quantum yield and the CPL properties of 1 indicate its potential application as a CPL emitter.
通过二茂铁盐钴介导氧化2,2'-二锂-1,1'-联萘的一锅法制备了萘的手性环状六聚体[6]环-1,2-萘（1）。通过单晶X射线晶体学和核磁共振分析确定了1的分子结构，揭示了其具有近似D对称性的环状结构。化合物1在383 nm处呈现蓝色发射，光致发光量子产率高达97%，这可归因于其刚性的十二元环结构。通过手性高效液相色谱对1进行光学拆分，从而评估其手性光学性质。每个对映体都表现出具有复杂科顿效应的圆二色性，这些效应可分为三个正或三个负的偶合。在383 nm处观察到圆偏振发光，各向异性因子|g|约为10。1的高光致发光量子产率和圆偏振发光性质表明其作为圆偏振发光发射体具有潜在应用价值。
