Evolving Fluorophores into Circularly Polarized Luminophores with a Chiral Naphthalene Tetramer: Proposal of Excimer Chirality Rule for Circularly Polarized Luminescence
Evolving Fluorophores into Circularly Polarized Luminophores with a Chiral Naphthalene Tetramer: Proposal of Excimer Chirality Rule for Circularly Polarized Luminescence
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DOI：
10.1021/jacs.9b02582
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发表时间：
2019-04-17
影响因子：
15
通讯作者：
Ema, Tadashi
中科院分区：
文献类型：
--
作者：
Takaishi, Kazuto;Iwachido, Kazuhiro;Ema, Tadashi
报道了一种将多种荧光多环芳烃转化为具有高g（lum）和Phi（FL）值的圆偏振发光（CPL）准分子染料的通用方法。该方法涉及在合成的最后一步通过酯键将具有六个荧光基团的手性季萘基功能化。对1-、2-和4-芘基、2-和3-苝酰和2-蒽基染料证明了这种方法的有效性。他们中的大多数是第一个或罕见的CPL染料的例子。在基态下，荧光团通过累积的空间和电子效应紧密排列。在激发态下，荧光团形成扭曲的准分子，维持基态构象。局部手性准分子直接影响CPL的性质。对cpl符号的系统研究使我们发现了一个称为准分子手性规则的规则：右手和左手准分子分别表现为(+)-和(-)- cpl。
A versatile method for converting various fluorescent polycyclic aromatic hydrocarbons into circularly polarized luminescence (CPL) excimer dyes with high g(lum) and Phi(FL) 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.