Regioisomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes
Regioisomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes
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基于多面体低聚倍半硅氧烷的区域异构串联三嵌段两亲物
DOI：
10.1002/chem.201800895
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Zhang Wen-Bin
中科院分区：
文献类型：
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作者：
Shao Yu;Yin Hang;Jin Peng-Fei;Jiang Yu-Sheng;Yang Shuguang;Zhang Wen-Bin
我们报道了一系列串联的三嵌段状两亲区域异构体的设计、合成和自组装，这些异构体由一个棒状含氟多面体低聚倍半硅氧烷(FPOSS)笼和两个球状叔丁基POSS笼(TBPOSS)组成，分别为对位、间位和邻位构型。通过连续的“点击”反应实现了精确的合成，并通过核磁共振、FT-IR和MALDI-TOF MS光谱组合技术对化合物进行了全面的表征。只有邻位异构体形成了由全氟烷基链结晶引起的有序片层结构，另外两个由于不利的区域构型阻碍了堆积而保持无定形。这三种区域异构体的不同组装行为反映了微小的结构差异对精确的大分子组装的微妙影响。
We report the design, synthesis and self‐assembly of a series of tandem triblock shape amphiphile regioisomers composed of one rod‐like fluorinated polyhedral oligomeric silsesquioxane (FPOSS) cage tethered with two sphericaltert‐butyl‐POSS (tBPOSS) cages inpara‐,meta‐, andortho‐configurations. Precision syntheses are achieved through sequential “click” reactions and the compounds are thoroughly characterized by combined techniques of NMR, FT‐IR and MALDI‐TOF MS spectroscopy. Only theortho‐isomer forms an ordered lamellae structure induced by the crystallization of perfluoroalkyl‐chains and the other two remain amorphous due to frustrated packing by unfavorable regio‐configuration. The distinct assembly behaviors of these three regioisomers reflect the delicate influence of a minute structural difference on precision macromolecular assembly.