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From mononuclear to linear one-dimensional coordination species of copper(II)–chloranilate: design and characterization

Jurić, Marijana; Molčanov, Krešimir; Žilić, Dijana; Kojić-Prodić, Biserka (2016) From mononuclear to linear one-dimensional coordination species of copper(II)–chloranilate: design and characterization. RSC Advances, 6 (67). pp. 62785-62796. ISSN 2046-2069

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A series of six novel mononuclear, binuclear and linear one-dimensional (1D) compounds of copper(II) with chloranilic acid (3,6-dichloro-2,5-dihydroxybenzoquinone, H2CA) is prepared and a design strategy for the preparation of such complexes is discussed. Four described compounds are linear 1D coordination polymers [Cu(CA)]n, whereas another two involve a binuclear and a mononuclear, Cu2(CA)3 and Cu(CA)2, core unit. A linear polymer incorporating bulky aromatic imidazole has been synthesized as a result of investigation of the influence of pH on the reaction mixture. Two coordination modes of the chloranilate dianion are observed. The bridging (bis)bidentate mode generates linear 1D polymeric species. Among these one reveals square-pyramidal coordination of Cu2+, whereas the three polymers contain Cu2+ in an octahedral arrangement. However, the combination of both, terminal bidentate (ortho-quinone) and bridging (bis)bidentate modes of coordination produces a binuclear complex anion, which comprises a square-pyramidal coordination of Cu2+ complex anions forming a supramolecular honeycomb-like network encapsulating 4,4′-bipyridine cations. When the chloranilate dianion coordinates the Cu2+ atom only in a terminal bidentate mode, a mononuclear complex with an octahedral environment of the metal centre is formed. The presence of the bulky ancillary ligand imidazole produces an unprecedented packing involving chiral (racemic) and achiral (meso-compound) coordination polymers in the same crystal. Electron spin resonance spectroscopy of polycrystalline samples determined g-tensor parameters of copper(II) ions in different coordination geometries and revealed weak exchange interactions (|J| < 1 cm−1) in linear metal-complex polymers and dimeric species.

Item Type: Article
Uncontrolled Keywords: coordination polymer; chloranilic acid; crystal structure; crystal engineering
Subjects: NATURAL SCIENCES > Chemistry > Physical Chemistry
NATURAL SCIENCES > Chemistry > Inorganic Chemistry
Divisions: Division of Materials Chemistry
Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Novi metal-organsi sustavi s oksalatnim i kinoidnim ligandima s podešenim svojstvima pogodnim za primjenu-NMOSBOQLWTPSFPKrešimir MolčanovIP-09-2014-4079HRZZ
Karakterizacija niskotemperaturne molekulske dinamike sustava s neuređenom rešetkom metodom ESR-DESiReMarina Ilakovac KvederIP-11-2013-1108HRZZ
Depositing User: Krešimir Molčanov
Date Deposited: 06 Apr 2017 11:01
DOI: 10.1039/C6RA13809H

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