Department of Material and Life Chemistry, Kanagawa University, 3-2-7 Rokkakubashi, Yokohama, 221-8686, Japan.
Division of Materials Science, Nara Institute of Science and Technology, Ikoma, Nara, 630-0192, Japan.
Chempluschem. 2020 Apr;85(4):619-626. doi: 10.1002/cplu.201900615. Epub 2019 Dec 13.
Systems that show circularly polarized luminescence (CPL) are usually constructed in one of two possible ways: either covalently binding the chiral moieties (usually organic compounds) to luminophores (inorganic or organic compounds) or associating the luminophores as guests with chiral hosts (usually organic compounds). Herein, we propose inorganic-based CPL-active systems constructed by the "chiral host-luminescent guest" strategy, in which silica acts as a chiral host to endow various luminescent guests with CPL. The chiral silica was modified by silane coupling with amino or phenyl groups to allow interaction with luminescent guests, and then used in combination with acidic achiral dyes, lead-halide type perovskites, and aggregation-induced emission luminogens (AIEgens). Interestingly, when these achiral guests were noncovalently confined in surface-modified chiral silica, the guests showed chiroptical behavior in the circular dichroism (CD) spectra, and thus became CPL active, even though they are not inherently chiral. The surface functional groups on the silica play very important roles in transferring the chiral information from the silica to the guests. This work provides a new concept for constructing CPL-active systems using inorganic materials as a chiral source.
具有圆偏振发光(CPL)的体系通常可以通过以下两种方式之一构建:将手性部分(通常为有机化合物)共价键合到发光体(无机或有机化合物)上,或将发光体作为客体与手性主体(通常为有机化合物)缔合。在此,我们提出了通过“手性主体-发光客体”策略构建的基于无机的 CPL 活性体系,其中二氧化硅作为手性主体赋予各种发光客体 CPL。通过硅烷偶联带有氨基或苯基的手性硅来修饰手性二氧化硅,使其能够与发光客体相互作用,然后与酸性非手性染料、卤化铅钙钛矿和聚集诱导发光(AIE)发光体结合使用。有趣的是,当这些非手性客体非共价地被限制在表面修饰的手性硅中时,客体在圆二色性(CD)光谱中表现出手性行为,从而变得具有 CPL 活性,尽管它们本身并不具有手性。二氧化硅表面上的功能基团在手性信息从二氧化硅传递到客体中起着非常重要的作用。这项工作为使用无机材料作为手性源构建 CPL 活性体系提供了一个新概念。