Roose Jesse, Leung Anakin Chun Sing, Wang Jia, Peng Qian, Sung Herman H-Y, Williams Ian Duncan, Tang Ben Zhong
HKUST-Shenzhen Research Institute , No. 9 Yuexing 1st RD , South Area , High-tech Park , Nanshan , Shenzhen 518057 , China . Email:
Department of Chemistry , Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration & Reconstruction , Institute for Advanced Study , Institute of Molecular Functional Materials , Division of Biomedical Engineering , Division of Life Science and State Key Laboratory of Molecular Neuroscience , The Hong Kong University of Science & Technology , Clear Water Bay , Kowloon , Hong Kong , China.
Chem Sci. 2016 Sep 1;7(9):6106-6114. doi: 10.1039/c6sc01614f. Epub 2016 Jun 2.
We present a conceptually new approach to synthesise a boron-containing Aggregation-Induced Emissive Luminogen (AIEgen) with a chiral chromophore. An intramolecular N-B coordinating bond results in a low-energy transition that renders the material red-emissive in a solid state. By competitive binding of nucleophiles to the boron atom, this bond is replaced in favour of an intermolecular coordinating bond, which results in a tremendous blue-shift in both the absorption and emission. A supportive DFT computation elucidates that a breakage of the intramolecular N-B coordinating bond causes a tremendous loss of conjugation in the LUMO, resulting in a larger energy gap. Owing to the fact that our scaffold is intrinsically chiral and Lewis-acidic, we demonstrate how our AIEgen discriminates between two pairs of enantiomers in a simple UV-vis measurement. Furthermore, the binding capabilities are exploited to stain polymer blends that comprised a non-coordinating and a Lewis-basic polymer. The red fluorescence that originates only from domains of the non-coordinating polymer is conveniently detected by a fluorescence microscope. Thus, compared to current analytical methods, we present a cheaper and faster methodology to study the micro-morphologies of certain polymer blends.
我们提出了一种概念上全新的方法来合成一种含硼的具有手性发色团的聚集诱导发光发光体(AIEgen)。分子内的N-B配位键导致低能跃迁,使该材料在固态下呈红色发光。通过亲核试剂与硼原子的竞争性结合,这种键被取代,转而形成分子间配位键,这导致吸收和发射都发生巨大的蓝移。支持性的密度泛函理论(DFT)计算表明,分子内N-B配位键的断裂会导致最低未占分子轨道(LUMO)中共轭的巨大损失,从而导致更大的能隙。由于我们的支架本质上是手性的且具有路易斯酸性,我们展示了我们的AIEgen如何在简单的紫外-可见测量中区分两对对映体。此外,利用其结合能力对由非配位聚合物和路易斯碱性聚合物组成的聚合物共混物进行染色。仅来自非配位聚合物区域的红色荧光可通过荧光显微镜方便地检测到。因此,与当前的分析方法相比,我们提出了一种更便宜、更快的方法来研究某些聚合物共混物的微观形态。