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聚集诱导的手性光生以及具有左旋和右旋螺旋聚硅烷的非手性偶氮苯-芴共聚物的光致开关

Aggregation-induced chiroptical generation and photoinduced switching of achiral azobenzene--fluorene copolymer endowed with left- and right-handed helical polysilanes.

作者信息

Chen Hailing, Yin Lu, Liu Meng, Wang Laibing, Fujiki Michiya, Zhang Wei, Zhu Xiulin

机构信息

Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University Suzhou Industrial Park Suzhou 215123 China

Division of Materials Science, Nara Institute of Science and Technology 8946-5, Takayama Ikoma Nara 630-0192 Japan

出版信息

RSC Adv. 2019 Feb 8;9(9):4849-4856. doi: 10.1039/c8ra09345h. eCollection 2019 Feb 5.

DOI:10.1039/c8ra09345h
PMID:35514644
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9060682/
Abstract

The left and right helicities of azobenzene (Azo)-containing main-chain polymer (PF8Azo) were successfully controlled with an enantiomeric pair of rigid rod-like helical polysilanes carrying ()- and ()-2-methylbutyl groups (PSi- and PSi-, respectively) as their hetero-aggregates in a mixture of chloroform and methanol solvents and in the solid state. Optimizing the good and poor cosolvents and their volume fractions showed that the molar ratio of PF8Azo to PSi-/- and the molecular weight of PF8Azo were crucial to boost the CD amplitudes of PF8Azo/PSi- and PF8Azo/PSi- hetero-aggregates. The photoresponsive - transformation caused noticeable changes in the sign and magnitude of the chiroptical behavior due to the hetero-aggregates. Moreover, the optically active PF8Azo homo-aggregates were produced by complete photoscissoring reactions at 313 nm, which could be assigned to the Siσ-Siσ* transitions of PSi- and PSi-.

摘要

在氯仿和甲醇混合溶剂以及固态状态下，通过携带（）-和（）-2-甲基丁基的对映体对刚性棒状螺旋聚硅烷（分别为PSi-和PSi-）作为其杂聚集体，成功控制了含偶氮苯（Azo）的主链聚合物（PF8Azo）的左右螺旋度。优化良溶剂和不良共溶剂及其体积分数表明，PF8Azo与PSi-/-的摩尔比以及PF8Azo的分子量对于提高PF8Azo/PSi-和PF8Azo/PSi-杂聚集体的圆二色性（CD）振幅至关重要。由于杂聚集体，光响应性的-转变导致手性光学行为的符号和幅度发生明显变化。此外，通过在313nm处进行完全光剪接反应产生了光学活性的PF8Azo均聚集体，这可归因于PSi-和PSi-的Siσ-Siσ*跃迁。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/130a30e4b720/c8ra09345h-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/b22accbf620f/c8ra09345h-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/7cfb25f2062c/c8ra09345h-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/4cea33928736/c8ra09345h-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/cc2b07469b73/c8ra09345h-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/37c9834c1c3e/c8ra09345h-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/935a9c980569/c8ra09345h-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/130a30e4b720/c8ra09345h-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/b22accbf620f/c8ra09345h-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/7cfb25f2062c/c8ra09345h-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/4cea33928736/c8ra09345h-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/cc2b07469b73/c8ra09345h-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/37c9834c1c3e/c8ra09345h-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/935a9c980569/c8ra09345h-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5939/9060682/130a30e4b720/c8ra09345h-f7.jpg

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Soft Matter. 2007 Sep 19;3(10):1312-1317. doi: 10.1039/b710165a.
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Chirality Construction from Preferred π-π Stacks of Achiral Azobenzene Units in Polymer: Chiral Induction, Transfer and Memory.聚合物中由非手性偶氮苯单元的优先π-π堆积构建手性：手性诱导、传递和记忆。
Polymers (Basel). 2018 Jun 4;10(6):612. doi: 10.3390/polym10060612.
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DNA-Guided Plasmonic Helix with Switchable Chirality.
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Ambidextrous Chirality Transfer Capability from Cellulose Tris(phenylcarbamate) to Nonhelical Chainlike Luminophores: Achiral Solvent-Driven Helix-Helix Transition of Oligo- and Polyfluorenes Revealed by Sign Inversion of Circularly Polarized Luminescence and Circular Dichroism Spectra.纤维素三（苯甲酰基）向非螺旋链状发光体的双折射手性传递能力：手性溶剂驱动寡聚芴和多芴的螺旋-螺旋转变，通过圆偏振发光和圆二色光谱的信号反转揭示。
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