Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state
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
© 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH.
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. ...
Publication in research information system
MetadataShow full item record
Additional information about fundingNMR spectra were recorded at the Center for Magnetic Resonance (St. Petersburg State University Research Park). T.E. and P.H. acknowledge grants of computer capacity from the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533 ).
Showing items with similar title or keywords.
Studies of Nature of Uncommon Bifurcated I–I···(I–M) Metal-Involving Noncovalent Interaction in Palladium(II) and Platinum(II) Isocyanide Cocrystals Bulatova, Margarita; Ivanov, Daniil M.; Rautiainen, J. Mikko; Kinzhalov, Mikhail A.; Truong, Khai-Nghi; Lahtinen, Manu; Haukka, Matti (American Chemical Society (ACS), 2021)Two isostructural trans-[MI2(CNXyl)2]·I2 (M = Pd or Pt; CNXyl = 2,6-dimethylphenyl isocyanide) metallopolymeric cocrystals containing uncommon bifurcated iodine···(metal–iodide) contact were obtained. In addition to classical ...
Non-conventional synthesis and photophysical studies of platinum(II) complexes with methylene bridged 2,2′-dipyridylamine derivatives Bulatov, Evgeny; Haukka, Matti (Royal Society of Chemistry, 2019)Methylene bridged 2,2′-dipyridylamine (dpa) derivatives and their metal complexes possess outstanding properties due to their inherent structural flexibility. Synthesis of such complexes typically involves derivatization ...
Katlenok, Eugenе A.; Haukka, Matti; Levin, Oleg V.; Frontera, Antonio; Kukushkin, Vadim Yurievich (Wiley-VCH Verlag, 2020)The theoretical data for the half‐lantern complexes [Pt(C^N)(μ‐S^N)] 2 ( 1 – 3 ; С^N is cyclometalated 2‐Ph‐benzothiazole; S^N is 2‐SH‐pyridine 1 , 2‐SH‐benzoxazole 2 , 2‐SH‐tetrafluorobenzothiazole 3 ) indicate that the ...
Ward, Jas S.; Frontera, Antonio; Rissanen, Kari (American Chemical Society (ACS), 2021)The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2′-bipyridyl) or bpyMe2 (4,4′-dimethyl-2,2′-dipyridyl), and a monodentate ligand L2, ...
Synthetic and structural studies of covalent and non-covalent interactions of ligands and metal center in platinum(II) complexes containing 2,2′- dipyridylamine or oxime ligands Bulatov, Evgeny (2019)Coordination compounds of platinum(II) have played an important role in the development of coordination chemistry, and even nowadays new aspects of their structural diversity and reactivity continue to emerge. Applications ...