Supramolecular Assembly of Metal Complexes by (Aryl)I⋯dz2[PtII] Halogen Bond
Katlenok, E. A., Haukka, M., Levin, O. V., Frontera, A., & Kukushkin, V. Y. (2020). Supramolecular Assembly of Metal Complexes by (Aryl)I⋯dz2[PtII] Halogen Bond. Chemistry : A European Journal, 26(34), 7692-7701. https://doi.org/10.1002/chem.202001196
Published inChemistry : A European Journal
© 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
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 Pt···Pt orbital interaction leads to an increment of the nucleophilicity of the outer d z 2 ‐orbitals to provide assembly with electrophilic species. 1 – 3 were co‐crystallized with bifunctional halogen bond (XB) donors to give adducts ( 1 – 3 ) 2 ∙(1,4‐diiodotetrafluorobenzene) and infinite polymeric [ 1 ·1,1’‐diiodoperfluorodiphenyl] n . X‐ray crystallography revealed that the supramolecular assembly is achieved via (Aryl)I∙∙∙ d z 2 [Pt II ] XB between iodine σ‐holes and lone pairs of the positively charged (Pt II ) 2 centers, acting as nucleophilic sites. The polymer includes a curved linear chain ···Pt 2 ···I(arene F )I···Pt 2 ··· involving XB between iodines of the perfluoroarene linkers and (Pt II ) 2 moieties. The 195 Pt NMR, UV‐vis, and CV studies indicate that XB is preserved in CH(D) 2 Cl 2 solutions. ...
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Additional information about fundingSupport of the synthetic work and compound characterizations from the Russian Foundation for Basic Research (grant 18-29-04006) is gratefully acknowledged. Electrochemical part of this work was supported by the Russian Foundation for Basic Research project 19-29-08026. E.A.K. is thankful to the Saint Petersburg State University for postdoctoral fellowship. Physicochemical studies were performed at the Center for Magnetic Resonance, Center for Xray Diffraction Studies, and Center for Chemical Analysis and Materials Research (all belonging to Saint Petersburg State University). V.Y.K. is grateful to South Ural State University (Act 211 Government of the Russian Federation, contract No 02.A03.21.0011) for putting facilities at his disposal. We are indebted to Prof. Dr. P.M. Tolstoy and Dr. D.M. Ivanov for valuable suggestions and Dr. A.V. Rozhkov for kind loan of 1,1’-FIDB and 2-mercapto4,5,6,7-tetrafluorobenzothiazole. ...
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