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