Temperature-Responsive Chiral (A)6B Supramolecular Cages Based on Conformational Preferences

Shi-Gui Chen; Zhi-Xiong Zhao; Xiao-Nan Jiang; Lu Wang; Tian-You Zhou; Cheng-Lu Lu; Xin Zhao; Xi-Kui Jiang; Yuguo Ma; Ren-Xiao Wang; Zhan-Ting Li

doi:10.1002/asia.201501090

Temperature-Responsive Chiral (A)6B Supramolecular Cages Based on Conformational Preferences

Chem Asian J. 2016 Feb 18;11(4):465-9. doi: 10.1002/asia.201501090. Epub 2015 Nov 25.

Authors

Shi-Gui Chen¹, Zhi-Xiong Zhao¹, Xiao-Nan Jiang¹, Lu Wang¹, Tian-You Zhou¹, Cheng-Lu Lu¹, Xin Zhao², Xi-Kui Jiang¹, Yuguo Ma³, Ren-Xiao Wang⁴, Zhan-Ting Li^{5

6}

Affiliations

¹ Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
² Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China. xzhao@mail.sioc.ac.cn.
³ Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China. ygma@pku.edu.cn.
⁴ Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China. wangrx@mail.sioc.ac.cn.
⁵ Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China. ztli@mail.sioc.ac.cn.
⁶ Department of Chemistry, Fudan University, 220 Handan Road, Shanghai, 200433, China. ztli@mail.sioc.ac.cn.

PMID: 26606400
DOI: 10.1002/asia.201501090

Abstract

Two chiral (A)6B-typed supramolecular cages were constructed from hydrogen-bonded C6 -symmetric zinc porphyrin hexamers and chiral C3-symmetric pyridyl hexadentates with a core of 1,3,5-triphenylbenzene. Circular dichroism and molecular simulations revealed that the symmetry of the supramolecular cages switched from pseudo-C3v to C3 with the rotational confinement of the biphenyl backbones at low temperatures, which generated conformationally chiral transfer and amplification. This unique phenomenon suggests a new strategy to develop smart materials with high sensitivity and excellent reversibility.

Keywords: chiral transfer; conformational chirality; conformational preference; supramolecular cages; temperature-responsive.