A mixed-valence copper chloride coordination polymer composed of one-dimensional cationic and anionic substructures

Hee Sun Park, Jae Chang Lee, Myung Hwa Jung, Yong Min Lee, Wonwoo Nam, Nam Hwi Hur

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Abstract

A new three-dimensional (3D) coordination polymer [{CuIICl2(Hdatrz)2}(CuI2Cl4)]n (1) that consists of two independent cationic and anionic substructures has been synthesized from the reaction of 3,5-diamino-1,2,4-triazole (datrz) with CuICl and CuIICl2. The cationic subunit, [CuIICl2(Hdatrz)2]2+, has a one-dimensional (1D) structure based on [CuIICl2(Hdatrz)2Cl2] octahedral units, while the anionic component [CuI2Cl4]2− consists of 1D chains of edge-sharing CuCl4 tetrahedra. The cationic and anionic chains are linked through interionic hydrogen bonding. The protonated datrz ligand plays an essential role in constructing the supramolecular framework. The magnetic CuII (d9) ion occupies the octahedral center of the cationic substructure, while the non-magnetic CuI (d10) ion resides in the tetrahedral core of the anionic substructure. The temperature-dependent magnetic susceptibility of 1 reveals a typical paramagnetic behavior, and the Curie-Weiss fit shows a magnetic moment of 2.04 μB per CuII. There is weak antiferromagnetic ordering below a Néel temperature of 2.46 K, presumably due to an antiferromagnetic interaction between neighboring CuII ions linked by two Cl ligands. The EPR spectra of 1 suggest that the [CuIICl2(Hdatrz)2Cl2] subunit has a tetragonally elongated octahedral geometry and the complex 1 contains mixed-valence CuI and CuII species. In addition, we discovered a novel molecular compound with a stoichiometry of (H2datrz)Cl2 (2), which was prepared by the reaction of concentrated hydrochloric acid with datrz in the absence of copper chlorides. X-ray crystal structure determination shows that the compound consists of an unusual di-protonated H2datrz2+ cation and two charge-compensating Cl anions.

Original languageEnglish
Pages (from-to)8354-8362
Number of pages9
JournalCrystEngComm
Volume24
Issue number48
DOIs
StatePublished - 16 Nov 2022

Bibliographical note

Funding Information:
This work (N. H. H.) was supported by the NRF funded by the Korean Government (MSIT) (grant no. NRF-2019R1A2C1003666) and the COMPA funded by the Korean Government (MSIT) (grant no. 2021-JDH-1-SB-1). This work (M. H. J.) was supported by the National Research Foundation of Korea (NRF) (grant no. 2020R1A2C3008044).

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

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