A1 Journal article (refereed)
Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen-Bonds (2020)

Shi, Q., Zhou, X., Yuan, W., Su, X., Neniškis, A., Wei, X., Taujenis, L., Snarskis, G., Ward, J. S., Rissanen, K., de Mendoza, J., & Orentas, E. (2020). Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen-Bonds. Journal of the American Chemical Society, 142(7), 3658-3670. https://doi.org/10.1021/jacs.0c00722

JYU authors or editors

Publication details

All authors or editors: Shi, Qixun; Zhou, Xiaohong; Yuan, Wei; Su, Xiaoshi; Neniškis, Algirdas; Wei, Xin; Taujenis, Lukas; Snarskis, Gustautas; Ward, Jas S; Rissanen, Kari; et al.

Journal or series: Journal of the American Chemical Society

ISSN: 0002-7863

eISSN: 1520-5126

Publication year: 2020

Volume: 142

Issue number: 7

Pages range: 3658-3670

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/jacs.0c00722

Research data link: https://pubs.acs.org/doi/suppl/10.1021/jacs.0c00722/suppl_file/ja0c00722_si_001.pdf

Publication open access: Not open

Publication channel open access: 

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/67591

Additional information: The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c00722.; Experimental procedures and spectroscopic data (PDF); https://pubs.acs.org/doi/suppl/10.1021/jacs.0c00722/suppl_file/ja0c00722_si_001.pdf
X-ray diffraction data files (CIF); https://pubs.acs.org/doi/suppl/10.1021/jacs.0c00722/suppl_file/ja0c00722_si_002.cif

Abstract

We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal coordinating 2,2’-bipyridine units. When mixed with metal ions such as Fe2+ or Zn2+, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal coordinating site results in a T-symmetric cage, whereas by introducing flexibility either through a methylene linker or rotating benzene ring allows the formation of S4-symmetric cages with self-filled interior. In addition, the possibility to select between tetrahedral cages or helicates, and to control the dimensions of the aggregate, has been demonstrated with three component assembly using external hydrogen-bonding molecular inserts or by varying the radius of the metal ion (Hg2+ vs Fe2+). Self-sorting studies of individual Fe2+ complexes of with ligands of different sizes revealed their inertness toward ligand scrambling.

Keywords: supramolecular chemistry; hydrogen bonds

Free keywords: synthesis; supramolecular monomers; hydrogen-bonds

Contributing organizations

Ministry reporting: Yes

VIRTA submission year: 2020

JUFO rating: 3