A1 Journal article (refereed)
Thermodynamically driven self-assembly of pyridinearene to hexameric capsules (2019)

Kiesilä, A., Beyeh, N. K., Moilanen, J. O., Puttreddy, R., Götz, S., Rissanen, K., Barran, P., Lützen, A., & Kalenius, E. (2019). Thermodynamically driven self-assembly of pyridinearene to hexameric capsules. Organic and Biomolecular Chemistry, 17(29), 6980-6984. https://doi.org/10.1039/C9OB01383K

JYU authors or editors

Kiesilä, Anniina
Moilanen, Jani
Puttreddy, Rakesh
Rissanen, Kari
Kalenius, Elina

Publication details

All authors or editors: Kiesilä, Anniina; Beyeh, Ngong Kodiah; Moilanen, Jani O.; Puttreddy, Rakesh; Götz, Sven; Rissanen, Kari; Barran, Perdita; Lützen, Arne; Kalenius, Elina

Journal or series: Organic and Biomolecular Chemistry

ISSN: 1477-0520

eISSN: 1477-0539

Publication year: 2019

Volume: 17

Issue number: 29

Pages range: 6980-6984

Publisher: Royal Society of Chemistry

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1039/C9OB01383K

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/65411

Abstract

Pyridinearene macrocycles have previously shown unique host–guest properties in their capsular dimers including endo complexation of neutral molecules and exo complexation of anions. Here, we demonstrate for the first time the formation of hydrogen bonded hexamer of tetraisobutyl-octahydroxypyridinearene in all three states of matter – gas phase, solution and solid-state. Cationic tris(bipyridine)ruthenium(II) template was found to stabilize the hexamer in gas phase, whereas solvent molecules do this in condensed phases. In solution, the capsular hexamer was found to be the thermodynamically favoured self-assembly product and transition from dimer to hexamer occurred in course of time. The crystal structure of hexamer revealed 24 N–H⋯O direct intermolecular hydrogen bonds between the six pyridinearene macrocycles without any bridging solvent molecules. Hydrogen bond patterns correlate well with DFT computed structures. Thus, all structural chemistry methods (IM-MS, DOSY NMR, DFT, X-ray crystallography) support the same structure of the hexameric capsule that has a diameter of ca. 3 nm and volume of 1160 Å3.

Keywords: supramolecular chemistry; hydrogen bonds

Fields of science: