A1 Journal article (refereed)
Confinement Inside a Crystalline Sponge Induces Pyrrole to Form N−H⋅⋅⋅π Bonded Tetramers (2021)

Wu, M., Zhang, J., Yuan, L., Rissanen, K., & Pan, F. (2021). Confinement Inside a Crystalline Sponge Induces Pyrrole to Form N−H⋅⋅⋅π Bonded Tetramers. Chemistry: A European Journal, 27(38), 9814-9819. https://doi.org/10.1002/chem.202100087

JYU authors or editors

Publication details

All authors or editors: Wu, Mengling; Zhang, Junle; Yuan, Liangqian; Rissanen, Kari; Pan, Fangfang

Journal or series: Chemistry: A European Journal

ISSN: 0947-6539

eISSN: 1521-3765

Publication year: 2021

Publication date: 09/04/2021

Volume: 27

Issue number: 38

Pages range: 9814-9819

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/chem.202100087

Publication open access: Not open

Publication channel open access: 

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/75029

Abstract

Based on the DFT‐level calculated molecular volume (V mol ) of pyrrole and its liquid density, pyrrole manifests the highest liquid density coefficient LD c (defined as [V mol • density • 0.6023]/FW) value of 0.7. Normal liquids have LD c < 0.63. This very high LD c is due to the strong N‐H … π interactions in solution and hence pyrrole can be considered to be a pseudo‐crystalline liquid. When trapped inside the confined space of the crystalline sponge a reorientation of the N‐H … π interaction is observed leading to specific cyclic N‐H … π tetramers and N‐H … π dimers, verified by single crystal X‐ray crystallographic and computational methods. These tetramers are of the same size as four pyrrole molecules in the solid‐state of pyrrole, yet the cyclic N‐H … π intermolecular interactions are circularly oriented instead of the linear zig‐zag structure found in the X‐ray structure of a solid pyrrole. The confinement thus acts as an external driving force for the tetramer formation.

Keywords: amines; polymerism; supramolecular chemistry; chemical bonds; x-ray crystallography

Free keywords: aggregatio; confinement effect; crystalline sponge method; host-guest chemistry; pyrrole tetramer

Contributing organizations

Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 2