Division of Applied Chemistry, Graduate School of Natural Science and Technology , Okayama University , Tsushima, Okayama 700-8530 , Japan.
Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory , RIKEN , Hirosawa, Wako , Saitama 351-0198 , Japan.
J Am Chem Soc. 2019 Apr 17;141(15):6185-6190. doi: 10.1021/jacs.9b02582. Epub 2019 Apr 8.
A versatile method for converting various fluorescent polycyclic aromatic hydrocarbons into circularly polarized luminescence (CPL) excimer dyes with high g and Φ values is reported. This method involves the functionalization of a chiral quaternaphthyl with six fluorophores via ester linkages in the last step of the synthesis. The usefulness of this approach was demonstrated for 1-, 2-, and 4-pyrenyl, 2- and 3-perylenyl, and 2-anthryl dyes. Most of them are the first or rare examples of CPL dyes. In the ground state, the fluorophores are tightly arranged by cumulative steric and electronic effects. In the excited state, the fluorophores form a twist excimer that maintains the ground-state conformations. The local chiral excimer directly affected the CPL properties. The systematic study on the signs of the CPLs allowed us to find a rule called the excimer chirality rule: right- and left-handed excimers exhibit (+)- and (-)-CPL, respectively.
本文报道了一种将各种荧光多环芳烃转化为具有高 g 值和 Φ 值的圆偏振发光（CPL）激基染料的通用方法。该方法涉及通过酯键将手性四萘基与六个荧光团在合成的最后一步进行功能化。该方法在 1-、2-和 4-芘基、2-和 3-苝基以及 2-蒽基染料中得到了验证。其中大多数是 CPL 染料的首例或罕见实例。在基态下，荧光团受累积的立体和电子效应的紧密排列。在激发态下，荧光团形成扭曲激基复合物，保持基态构象。局部手性激基复合物直接影响 CPL 性质。对 CPL 符号的系统研究使我们能够找到一个称为激基手性规则的规则：右手和左手激基复合物分别表现出（+）-和（-）-CPL。
