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Facile synthesis of paramagnetic Co(II)-hexaborate(2-)-based semi-organic complexes: a combined investigation on X-ray crystal structure, Hirshfeld surfaces analysis, optical and magnetic properties

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Abstract

Two new paramagnetic hybrid cobalt(II)-hexaborate(2-)-based semi-organic complexes: (2A3MP)2[Co{κ3O–B6O7(OH)6}2].2H2O (1) and (2A4MP)2[Co{κ3O–B6O7(OH)6}2].2H2O (2) (2A3MP = 2-amino-3-methylpyridinium, 2A4MP = 2-amino-4-methylpyridinium) have been obtained and characterized by X-ray diffraction, FT-IR, TG–DTA, optical and magnetic measurements. X-ray diffraction revealed two isostructural compounds based on Co(II) complexes of bis(κ3O-donor hexaborate(2-)) ligands, [Co{κ3O–B6O7(OH)6}2]2−, differing only in the organic counter cation. The hydrated oxidopolyborate anions are extensively H-bounded to form 3D-porous supramolecular anionic frameworks. In both 1 and 2 isostructures, 2A3MP and 2A4MP cations are present in the created voids of the inorganic frameworks through a set of H-bonds with 58.5 and 60.5% H…O/O…H intercontact contributions, respectively, for 1 and 2 as confirmed by Hirshfeld surfaces analysis. The optical band gap of Co(II) complexes ranges between 2.72 and 2.82 eV. Both compounds exhibited well-resolved paramagnetic properties with magnetic susceptibility values ranging between 0.9552 cm3 mol−1 (at 2 K) and 0.0088 cm3 mol−1 (at 300 K), typical of octahedral Co(II) complexes.

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Data availability

All relevant data generated or analyzed during this study are included in this published article. CCDC 2153000 and 2,153,011 contain supplementary crystallographic data for 1 and 2, respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.htmlor the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+ 44) 1223–336-033; or e-mail: deposit@ccdc.cam.ac.uk.

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Acknowledgements

The authors are extremely thankful to the Department of Chemistry, University of Carthage, Faculty of Sciences of Bizerte for providing necessary facilities. Claire Minaud and Angel Arévalo-Lopez are also thanked for useful discussion on the magnetism.

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The authors declare that no funds, grants or other support were received during the preparation of this manuscript.

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Authors and Affiliations

  1. Laboratoire de Chimie des Matériaux LR13ES08, Faculté des Sciences de Bizerte, Université de Carthage, Zarzouna, 7021, Bizerte, Tunisia

    Ibrahim Karoui, Ahlem Maalaoui, Mohamed Rzaigui & Samah Akriche

  2. Unité de Catalyse et Chimie du Solide (UCCS), UMR CNRS 8181, Université de Lille, Centrale Lille, Univ. Artois, 59000, Lille, France

    Sylvain Duval

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  1. Ibrahim Karoui
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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by BK, AM, MR, SA and SD. The first draft of the manuscript was written by BK, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Samah Akriche.

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Karoui, I., Maalaoui, A., Duval, S. et al. Facile synthesis of paramagnetic Co(II)-hexaborate(2-)-based semi-organic complexes: a combined investigation on X-ray crystal structure, Hirshfeld surfaces analysis, optical and magnetic properties. Transit Met Chem 48, 365–375 (2023). https://doi.org/10.1007/s11243-023-00549-4

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