Stimuli-responsive conjugated polymers. Synthesis and chiroptical properties of polyacetylene carrying l-glutamic acid and azobenzene in the side chain
Stimuli-responsive conjugated polymers. Synthesis and chiroptical properties of polyacetylene carrying l-glutamic acid and azobenzene in the side chain
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DOI：
10.1016/j.polymer.2006.02.022
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发表时间：
2006-04
期刊：
影响因子：
4.6
通讯作者：
Haichao Zhao;F. Sanda;T. Masuda
中科院分区：
文献类型：
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作者：
Haichao Zhao;F. Sanda;T. Masuda
合成了一种含谷氨酸和偶氮苯的新型N-炔丙基酰胺（S）-CHCCH 2 NHCOCH（CH 2 CH 2 CO2 CH 2 C6 H5）NHCO 2 CH 2 CH 2-p-C6 H4 NNC 6 H5（1），并以（nbd）Rh+[η6-C6 H5 B-（C6 H5）3]为催化剂进行聚合，以93%的产率获得相应的聚合物[poly（1）]，其具有中等数均分子量12，200。手性光学研究表明，聚（1）在THF、CHCl_3、CH_2Cl_2和甲苯中呈螺旋结构。聚（1）经历溶剂和热驱动的螺旋-螺旋转变。侧链的反式偶氮苯在紫外光照射下异构化为顺式，同时螺旋度降低。在可见光照射下，顺式偶氮苯部分重新异构化为反式，而聚合物没有恢复原来的螺旋度。
A glutamic acid- and azobenzene-containing novel N-propargylamide, (S)-CHCCH2NHCOCH(CH2CH2CO2CH2C6H5)NHCO2CH2CH2–p–C6H4NNC6H5(1) was synthesized and polymerized with (nbd)Rh+[η6-C6H5B−(C6H5)3] as a catalyst to obtain the corresponding polymer [poly(1)] with the moderate number-average molecular weight of 12,200 in 93% yield. The chiroptical studies revealed that poly(1) took a helical structure in THF, CHCl3, CH2Cl2and toluene. Poly(1) underwent solvent and heat-driven helix–helix transition. The trans-azobenzene of the side chain isomerized into cis upon UV-irradiation, accompanying decrease in helicity. The cis-azobenzene moiety reisomerized into trans upon visible-light irradiation, while the polymer did not recover the original helicity.