A1 Journal article (refereed)
Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds (2023)

Yu, S., Truong, K.-N., Siepmann, M., Siiri, A., Schumacher, C., Ward, J. S., & Rissanen, K. (2023). Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds. Crystal Growth and Design, 23(2), 662-669. https://doi.org/10.1021/acs.cgd.2c01162

JYU authors or editors

Yu, Shilin
Truong, Khai-Nghi
Siepmann, Marcel
Ward, James
Rissanen, Kari

Publication details

All authors or editors: Yu, Shilin; Truong, Khai-Nghi; Siepmann, Marcel; Siiri, Arto; Schumacher, Christian; Ward, Jas S.; Rissanen, Kari

Journal or series: Crystal Growth and Design

ISSN: 1528-7483

eISSN: 1528-7505

Publication year: 2023

Publication date: 23/01/2023

Volume: 23

Issue number: 2

Pages range: 662-669

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.cgd.2c01162

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/85311

Abstract

A series of LH[Z–I–Z] halogen(I) complexes, where Z = saccharinato or phthalimido anions and LH = pyridinium, pyrazinium, tetrabutyl (TBA)- or tetramethylammonium (TMA) cations, were prepared, structurally characterized, and discussed as complexes consisting of a [N–I–N]− anion with a three-center–four-electron (3c-4e) halogen bond, and a hydrogen-bonding (pyridinium or pyrazinium) or inert (TBA or TMA) cation. The symmetric [N–I–N]− anion, reminiscent of the triiodide [I–I–I]− anion, is found to be structurally equivalent to its cationic analogue [N–I–N]+ with N–I bond lengths of 2.26 Å. In contrast to the homoleptic [N–I–N]+ complexes, asymmetry of the N–I bond lengths (2.21 and 2.28 Å) was observed for those [N–I–N]− complexes which manifested a hydrogen bond to only one saccharinato moiety, thus being structurally analogous to the asymmetric heteroleptic [N–I–N]+ complexes. The results show that the 3c-4e [N–I–N] halogen bond, being either positively or negatively charged, can be asymmetrized by an external hydrogen bond ([N–I–N]−) or by using two different ligands (heteroleptic [N–I–N]+).

Keywords: coordination complexes; halogens; iodine; chemical bonds

Fields of science: