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Designing antiferromagnetically coupled mono-, di- and tri-bridged copper(ii)-based catecholase models by varying the ‘Auxiliary Parts’ of the ligand and anionic co-ligand

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Abstract

Three Schiff base ligands were synthesized via condensation between 2,6-diformyl-4-R-phenol [where R = tert-butyl (HL1), iso-propyl (HL2), and chloro (HL3)] and N,N-dimethylethylene-1,2-diamine to prepare a series of copper(II) complexes. [Cu2(L1)(OH)(ClO4)](ClO4) (1) and [Cu2(L1)(SCN)3] (2) were synthesized from HL1, whereas [Cu2(L2)(SCN)2](ClO4) (3) and [Cu2(L3)(N3)(ClO4)](ClO4) (4) were obtained from the ligands HL2 and HL3, respectively. All the complexes were characterized by the usual physico-chemical techniques (FT-IR, UV-vis, single-crystal XRD, ESI-MS, 1H NMR and EPR) and their variable temperature magnetic study was also carried out. Single-crystal XRD analysis proved that a phenoxyl bridge was present in all four complexes. Complexes 1 and 4 contained additional bridges as hydroxo and μ1,1-azido ligands, respectively, together with perchlorate species to generate new binuclear CuII complexes containing a triple-mixed bridge. Complex 2 formed a thiocyanate-bridged polymeric chain. Interestingly, a polymeric chain was also formed via the participation of perchlorate ions in the case of complex 3 although thiocyanate, a better bridging anion, was present as a pending co-ligand. The influence of the ‘auxiliary part’ of the ligands, i.e., the ‘R’ group towards the structural diversity of complexes 1–4 was evaluated with the help of a DFT study. A magnetic study revealed the fact that the copper centres were antiferromagnetically coupled in all four complexes. The catecholase activities of all four complexes were determined in a DMSO medium and complex 4 was found to be inactive. The order of the catecholase activity of the remaining three complexes was 1 < 23. The trend of the catecholase activity was explained with the help of an ESI-MS study.

Graphical abstract: Designing antiferromagnetically coupled mono-, di- and tri-bridged copper(ii)-based catecholase models by varying the ‘Auxiliary Parts’ of the ligand and anionic co-ligand

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Publication details

The article was received on 17 Jul 2019, accepted on 14 Oct 2019 and first published on 14 Oct 2019


Article type: Paper
DOI: 10.1039/C9CE01115C
CrystEngComm, 2019, Advance Article

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    Designing antiferromagnetically coupled mono-, di- and tri-bridged copper(II)-based catecholase models by varying the ‘Auxiliary Parts’ of the ligand and anionic co-ligand

    S. Dasgupta, P. Chakraborty, P. Kundu, H. Kara, G. Aullón, E. Zangrando and D. Das, CrystEngComm, 2019, Advance Article , DOI: 10.1039/C9CE01115C

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