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Supramolecular Assembly of Metal Complexes by (Aryl)I⋅⋅⋅dz2 [PtII] Halogen Bonds

The theoretical data for the half‐lantern complexes [{Pt(CN^ )(μ‐SN^ )}2] [1–3; CN^ is cyclometalated 2‐Ph‐benzothiazole; SN^ is 2‐SH‐pyridine (1), 2‐SH‐benzoxazole (2), 2‐SH‐tetrafluorobenzothiazole (3)] indicate that the Pt⋅⋅⋅Pt orbital interaction increases the nucleophilicity of the outer dz2 or...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-06, Vol.26 (34), p.7692-7701
Main Authors: Katlenok, Eugene A., Haukka, Matti, Levin, Oleg V., Frontera, Antonio, Kukushkin, Vadim Yu
Format: Article
Language:English
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Summary:The theoretical data for the half‐lantern complexes [{Pt(CN^ )(μ‐SN^ )}2] [1–3; CN^ is cyclometalated 2‐Ph‐benzothiazole; SN^ is 2‐SH‐pyridine (1), 2‐SH‐benzoxazole (2), 2‐SH‐tetrafluorobenzothiazole (3)] indicate that the Pt⋅⋅⋅Pt orbital interaction increases the nucleophilicity of the outer dz2 orbitals to provide assembly with electrophilic species. Complexes 1–3 were co‐crystallized with bifunctional halogen bonding (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 through (Aryl)I⋅⋅⋅dz2 [PtII] XBs between iodine σ‐holes and lone pairs of the positively charged (PtII)2 centers acting as nucleophilic sites. The polymer includes a curved linear chain ⋅⋅⋅Pt2⋅⋅⋅I(areneF)I⋅⋅⋅Pt2⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (PtII)2 moieties. The 195Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D)2Cl2 solutions. Shedding light: Half‐lantern dz2[PtII2] complexes in which the PtII2 center exhibits increased nucleophilicity of the outer orbitals were assembled with symmetric diiodoperfluoroarene halogen bonding (XB) donors to give extended supramolecular arrays formed through (Aryl)I⋅⋅⋅dz2[PtII] XB, which were studied by XRD and by extensive theoretical calculations. Cyclic voltammetric, 195Pt NMR, and UV/Vis studies provided evidence that the XB is preserved in solution.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202001196