基于螺烯的新型手性有机分子笼
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摘要
有机分子笼是一类具有独特内在空腔的三维有机分子,在分子识别与分离、催化反应、气体吸附与存储等领域有着广阔的应用前景。有机分子笼的性能主要取决于骨架分子的化学结构与键合方式,而目前成功用于合成有机分子笼的前驱分子种类还比较有限,尤其是手性分子笼。近来,上海交通大学邱惠斌课题组以具有本征螺旋共轭结构的螺烯作为骨架分子,通过动态共价键等可逆键合过程,构建了一系列具有手性超级结构的有机分子笼,在手性识别与分离、圆偏振发光、手性分子开关等应用领域进行了积极探索。
Organic cages are a type of three-dimensional organic molecules with unique hollow structures, and show a wide range of potential applications in molecular recognition and separation, catalysis, gas adsorption and storage, etc. The function of these organic cages highly depends on the chemical structure and linkage of the molecular building blocks. However, it remains a challenge to expand the category of suitable molecular precursors, especially for chiral organic cages. Recently,Prof. Qiu Huibin and co-workers at Shanghai Jiao Tong University developed a new series of chiral organic cages using helicenes as building blocks. Chiral organic cages was synthesized via a process involving formation of reversible dynamic covalent bonds, and their chiral recognition and resolution, circularly polarized luminescence and molecular switching properties were investigated. In their current studies, a [3+2]-type cage was constructed adopting [6]helicene as the building blocks. Three helicene units were arranged in a propeller-like fashion, giving rise to an integrally triple-stranded helical structure for the cage skeleton. This structural chirality presented high stability in organic solvents as well, showing strong diastereotopy effect as observed from NMR spectra and unique structured circular dichroism signals. Besides, these chiral organic cages showed outstanding enantioselectivity against a series of small chiral molecules. The innovative strategy to construct organic cages using nonplanar, helical molecules as building blocks provided a new access to advanced functional organic porous materials.
Organic cages are a type of three-dimensional organic molecules with unique hollow structures, and show a wide range of potential applications in molecular recognition and separation, catalysis, gas adsorption and storage, etc. The function of these organic cages highly depends on the chemical structure and linkage of the molecular building blocks. However, it remains a challenge to expand the category of suitable molecular precursors, especially for chiral organic cages. Recently,Prof. Qiu Huibin and co-workers at Shanghai Jiao Tong University developed a new series of chiral organic cages using helicenes as building blocks. Chiral organic cages was synthesized via a process involving formation of reversible dynamic covalent bonds, and their chiral recognition and resolution, circularly polarized luminescence and molecular switching properties were investigated. In their current studies, a [3+2]-type cage was constructed adopting [6]helicene as the building blocks. Three helicene units were arranged in a propeller-like fashion, giving rise to an integrally triple-stranded helical structure for the cage skeleton. This structural chirality presented high stability in organic solvents as well, showing strong diastereotopy effect as observed from NMR spectra and unique structured circular dichroism signals. Besides, these chiral organic cages showed outstanding enantioselectivity against a series of small chiral molecules. The innovative strategy to construct organic cages using nonplanar, helical molecules as building blocks provided a new access to advanced functional organic porous materials.
引文
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[2]HASELL T,COOPER A I.Porous organic cages:Soluble,modular and molecular pores[J].Nature Reviews Materials,2016,1:16053.
[3]LIU X,LIU Y,LI G,et al.One-pot,18-component synthesis of an octahedral nanocontainer molecule[J].Angewandte Chemie International Edition,2006,45(6):901-904.
[4]HONG S,ROHMAN M R,JIA J,et al.Porphyrin boxes:Rationally designed porous organic cages[J].Angewandte Chemie International Edition,2015,54(45):13241-13244.
[5]SHEN Y,CHEN C F.Helicene:Synthesis and applications[J].Chemical Reviews,2012,112(3):1463-1535.
[6]GINGRAS M.One hundred years of helicene chemistry:Part 1.Non-stereoselective syntheses of carbohelicenes[J].Chemical Society Reviews,2013,42(3):968-1006.
[7]SALEH N,SHEN C,CRASSOUS J.Helicene-based transition metal complexes:Synthesis,properties and applications[J].Chemical Science,2014,5(10):3680-3694.
[8]MALIK A U,GAN F,SHEN C,et al.Chiral organic cages with a triple-stranded helical Structure derived from helicene[J].Journal of the American Chemical Society,2018,140(8):2769-2772.