Shao, Y.; Yin, H.; Jin, P.-F.; Jiang, Y.-S.; Yang, S.; Zhang, W.-B.* Regio-isomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes. Chem. Eur. J. 2018, 24 , 12389-12396. (Rated as Very Important Paper and Selected to the Young Chemists Special Issue)

Abstract: 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 spherical tert-butyl-POSS (tBPOSS) cages in para-, meta-, and orthoconfigurations. 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 the ortho-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.