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Three coordination polymers of manganese(II), cadmium(II) with a flexible ligand of cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid: crystal structures, thermal decomposition mechanisms and magnetic properties

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Abstract

The synthesized condition by means of controlling pH values of the reaction mixtures has been explored. Three Mn2+, Cd2+ ion coordination polymers with the fully deprotonated cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid (H4L) ligand were synthesized and characterized, sometimes incorporating different auxiliary ligand: {[Mn(H2O)6][Mn3(L)2(H2O)2]}·3H2O (1), [Cd2L(H2O)4] (2) and [Cd2Lphen)2(H2O)2]·3H2O (3) (phen = 1,10-phenanthroline). With an initial of pH values of 6.0, 4.0 and 9.0 of the reaction mixtures, we get the compounds 1, 2 and 3, respectively. In crystal of 1, two crystallographic different Mn2+ ions (Mn1 and Mn2) form a negatively charged coordination polymeric chain, which contains a centrosymmetrically linear trinuclear Mn2+ cluster (Mn3L2) subunit; another crystallographically independent Mn2+ ions (Mn3) coordinated by six water molecules act as counter ions to link the neighboring coordination polymeric chains via intermolecular H-bond interactions. The Mn2+ ions in 1 were completely replaced by Cd2+ ions to give 2 and 3, respectively. Complex 2 shows 3D distributions of Cd2+ ions while Complex 3 displays 2D networks contributed by intermolecular H-bond interactions. Three complexes exhibit distinct thermal decomposition mechanisms, and the deprotonated cis, cis, cis-1,2,3,4-cyclopentan-etetracarboxylic acid ligands decompose in 420–700 °C to give the residue MnO + C in 1 and CdO in 2 and in 3. Complex 1 shows a complicated magnetic behavior of coexistence of antiferromagnetic exchange interactions between neighboring Mn2+ ions.

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Acknowledgements

This work supported by Grants from the Natural Science Research Project of Anhui Provincial Department of Education (KJ2012B178, KJ2012ZD11, KJ2021A145), Science Research Project of Huangshan University (2012xkjq010) and the National Undergraduate Training Program for Innovation and Entrepreneurship (202010375004, 202010375015).

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Authors and Affiliations

  1. Department of Chemistry, Huangshan University, Huangshan, 245041, China

    Liang-Fang Huang, Zhao-Peng Qi & Chang-Jiang Li

  2. Key Laboratory of Inorgnic Functional Material, Huangshan University, Huangshan, 245041, China

    Liang-Fang Huang & Zhao-Peng Qi

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  1. Liang-Fang Huang
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Huang, LF., Qi, ZP. & Li, CJ. Three coordination polymers of manganese(II), cadmium(II) with a flexible ligand of cis, cis, cis-1,2,3,4-cyclopentanetetracarboxylic acid: crystal structures, thermal decomposition mechanisms and magnetic properties. Res Chem Intermed 48, 3867–3882 (2022). https://doi.org/10.1007/s11164-022-04784-9

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