Hybrid organic–inorganic supramolecular systems based on a pyridine end-decorated molybdenum(ii) halide cluster and zinc(ii) porphyrinate†
a
Anna A.
Sinelshchikova,
a
Gayane A.
Kirakosyan,
ad
Alexander G.
Martynov,
a
Mikhail S.
Grigoriev,
a
Dmitry A.
Piryazev,
bc
Maxim N.
Sokolov
*bc
and
Yulia G.
Gorbunova
*ad
Abstract
Herein, first examples of supramolecular hybrid organic–inorganic cluster-porphyrin [CPn (n = 2, 6)] systems constructed via metal–ligand coordination have been reported. The pyridine end-decorated Mo(II) halide cluster ((Bu4N)2[{Mo6I8}(OOC-C5H4N)6]), possessing remarkable photophysical properties, was chosen as the inorganic part and A2-type zinc porphyrin 5,15-bis[(p-tolyl)porphyrinato(2-)]zinc was selected as the organic part. The crystal structures of CP2 and CP6 hybrids have been characterised by single crystal X-ray diffraction. The CP2 complex is composed of two zinc porphyrins, coordinated to pyridyl moieties of the same cluster molecule, related by an inversion center. In the case of the CP6 complex, each cluster has three pairs of coordinated symmetrically equivalent zinc porphyrins. Also, the formation of supramolecular hybrid CPn (n = 2, 6) systems was unambiguously demonstrated in solution via NMR and UV-Vis spectroscopy titration and diffusion ordered NMR spectroscopy (DOSY).
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