Double-Layered Supramolecular Prisms Self-Assembled by Geometrically Non-equivalent Tetratopic Subunits

Heng Wang; Li-Peng Zhou; Yu Zheng; Kun Wang; Bo Song; Xuzhou Yan; Lukasz Wojtas; Xu-Qing Wang; Xin Jiang; Ming Wang; Qing-Fu Sun; Bingqian Xu; Hai-Bo Yang; Andrew C-H Sue; Yi-Tsu Chan; Jonathan L Sessler; Yang Jiao; Peter J Stang; Xiaopeng Li

doi:10.1002/anie.202010805

Double-Layered Supramolecular Prisms Self-Assembled by Geometrically Non-equivalent Tetratopic Subunits

Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1298-1305. doi: 10.1002/anie.202010805. Epub 2020 Nov 12.

Authors

Heng Wang¹, Li-Peng Zhou², Yu Zheng³, Kun Wang⁴, Bo Song⁵, Xuzhou Yan⁶, Lukasz Wojtas⁷, Xu-Qing Wang⁸, Xin Jiang⁹, Ming Wang⁹, Qing-Fu Sun², Bingqian Xu¹⁰, Hai-Bo Yang⁸, Andrew C-H Sue¹¹, Yi-Tsu Chan¹², Jonathan L Sessler¹³, Yang Jiao³, Peter J Stang¹⁴, Xiaopeng Li¹

Affiliations

¹ College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518055, China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
³ Department of Physics, Arizona State University, Tempe, AZ, 85287, USA.
⁴ Department of Physics and Astronomy, Department of Chemistry, Mississippi State University, Mississippi State, MS, 39762, USA.
⁵ Department of Chemistry, Northwestern University, Evanston, IL, 60208, USA.
⁶ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁷ Department of Chemistry, University of South Florida, Tampa, FL, 33620, USA.
⁸ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai, 200062, China.
⁹ State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin, 130012, China.
¹⁰ College of Engineering and Nanoscale Science and Engineering Center, University of Georgia, Athens, GA, 30602, USA.
¹¹ Institute for Molecular Design and Synthesis, School of Pharmaceutical Science & Technology, Tianjin University, Tianjin, 300072, China.
¹² Department of Chemistry, National (Taiwan) University, Taipei, 10617, Taiwan.
¹³ Department of Chemistry, The University of Texas, Austin, TX, 78712, USA.
¹⁴ Department of Chemistry, University of Utah, Salt Lake City, UT, 84112, USA.

PMID: 32946649
DOI: 10.1002/anie.202010805

Abstract

Supramolecular cages/vesicles in biology display sophisticated structures and functions by utilizing a few types of protein subunit quasi-equivalently at distinct geometrical locations. However, synthetic supramolecular cages still lack comparable complexity to reach the high levels of functionality found in natural systems. Herein we report the self-assembly of giant pentagonal supramolecular prisms (molecular weight >50 kDa) with tetratopic pyridinyl subunits serving different geometrical roles within the structures, and their packing into a novel superstructure with unexpected three-fold rotational symmetry in a single two-dimensional layer of crystalline state. The formation of these complicated structures is controlled by both the predetermined angles of the ligands and the mismatched structural tensions created from the multi-layered geometry of the building blocks. Such a self-assembly strategy is extensively used by viruses to increase the volume and complexity of capsids and would provide a new approach to construct highly sophisticated supramolecular architectures.

Keywords: geometrically non-equivalent subunits; pentagonal packing; self-assembly; supramolecular prisms.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.