A1 Journal article (refereed)
Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state (2021)

Bulatov, E., Eskelinen, T., Ivanov, A. Y., Tolstoy, P. M., Kalenius, E., Hirva, P., & Haukka, M. (2021). Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state. ChemPhysChem, 22(20), 2044-2049. https://doi.org/10.1002/cphc.202100468

JYU authors or editors

Publication details

All authors or editors: Bulatov, Evgeny; Eskelinen, Toni; Ivanov, Alexander Yu.; Tolstoy, Peter M.; Kalenius, Elina; Hirva, Pipsa; Haukka, Matti

Journal or series: ChemPhysChem

ISSN: 1439-4235

eISSN: 1439-7641

Publication year: 2021

Publication date: 30/07/2021

Volume: 22

Issue number: 20

Pages range: 2044-2049

Publisher: Wiley

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/cphc.202100468

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/78265

Abstract

Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I∙∙∙Pt∙∙∙I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I∙∙∙Pt∙∙∙I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.

Keywords: platinum; iodine; ligands; chemical compounds; physical chemistry

Free keywords: noncovalent interactions; axial interactions; excited states

Contributing organizations

Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 1