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A concerted evolution of supramolecular interactions in a {cation; metal complex; π-acid; solvent} anion-π system

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Abstract

Combined Single-Crystal XRD, solution 13C and 195Pt NMR, solid-state 195Pt NMR and UV-vis measurements, together with comprehensive (TD)DFT calculations, are used to describe the supramolecular interactions and sequential concerted structural transformation occurring in a {PPh4+;[Pt(CN)4]2−;TCP;CH2Cl2} supramolecular system (TCP – tetracyanopyrazine). In the solid-state, a mixture of needle-like co-crystals first appears, (PPh4)2{[TCP][Pt(CN)4]} (1) and (PPh4)2{[TCP][Pt(CN)4]}·2CH2Cl2 (2), and subsequent recrystallization leads to block-shaped co-crystals of (PPh4)2{[TCP]2[Pt(CN)4]}·2CH2Cl2 (3), wherein double {[Pt(CN)4]2−;TCP} and triple {[Pt(CN)4]2−;TCP;CH2Cl2} and {PPh4+;[Pt(CN)4]2−;TCP} synthons present either in 1 or 2 are reproduced in 3. The structural pathway (1,2 3) is accompanied by a 1D-to-2D modular evolution of anion-π interactions between [Pt(CN)4]2− and π-acidic TCP that seems to be driven, as indicated by calculations, not by maximizing their strength but rather by optimizing other crystal interactions, e.g. between PPh4+ cations. Formation of the corresponding {[Pt(CN)4]2−;π-acid} anion-π contacts in solution is evidenced by 13C NMR shifts and by new low-energy electronic absorption in the visible region (UV-vis). Finally, a combined solution/solid-state 195Pt NMR approach is used for the first time to shed light on the geometry and interactions involving such aggregates; it shows that the degree of trapping of [Pt(CN)4]2− near a π-acidic surface can be monitored by 195Pt NMR chemical shifts. The results give fresh insight into block arrangement tactics and characterization of hybrid organic-inorganic co-crystal salts, and into aggregation controlled properties.

Graphical abstract: A concerted evolution of supramolecular interactions in a {cation; metal complex; π-acid; solvent} anion-π system

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Supplementary files

Article information


Submitted
22 Jan 2020
Accepted
06 Mar 2020
First published
10 Mar 2020

Inorg. Chem. Front., 2020, Advance Article
Article type
Research Article

A concerted evolution of supramolecular interactions in a {cation; metal complex; π-acid; solvent} anion-π system

E. Kuzniak, J. Hooper, M. Srebro-Hooper, J. Kobylarczyk, M. Dziurka, B. Musielak, D. Pinkowicz, J. Raya, S. Ferlay and R. Podgajny, Inorg. Chem. Front., 2020, Advance Article , DOI: 10.1039/D0QI00101E

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