Azido derivatives of dinuclear copper(II) and 1D polynuclear nickel(II) complexes containing an unsymmetrical bidentate

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Azido derivatives of dinuclear copper(II) and 1D polynuclear nickel(II) complexes containing an unsymmetrical bidentate amine: synthesis, crystalline architecture, and magnetic behavior Habibar Chowdhury1 · Corrado Rizzoli2 · Chandan Adhikary3 Received: 29 July 2020 / Accepted: 29 September 2020 © Springer Nature Switzerland AG 2020

Abstract Dinuclear copper(II) complex [­ Cu2(L)2(μ2-1,1-N3)2(N3)2] (1) with double μ1,1-azido bridges and polynuclear nickel(II) complex [Ni(L)(μ2-1,1-N3)(μ2-1,3-N3)]n (2) with alternate double μ1,1-azido and μ1,3-azido bridges [L = 1-amino-2-(dimethylamino) ethane, N−3  = azide ion] have been synthesized and were characterized by physicochemical and spectroscopic methods. X-ray structural analysis revealed that each Cu(II) center of 1 adopts a distorted square-pyramidal geometry with a C ­ uN5 chromophore ligated through two N atoms of L, two N atoms of double bridging (μ1,1-N3), and one N atom of terminal azide ion. On the other hand, each Ni(II) center around the asymmetric unit of 2 adopts a distorted octahedral geometry with a ­NiN6 chromophore ligated through two N atoms of L, two N atoms of double μ1,1-N3, and two N atoms of double μ1,3-N3 bridges. The adjacent nickel centers are connected to alternate double μ1,1-N3 and double μ1,3-N3 bridges, affording a onedimensional (1D) polymeric chain structure. Temperature-dependent magnetic susceptibility measurements evidenced a dominant antiferromagnetic interaction between the metal centers of both complexes 1 and 2.

Introduction The preparation of coordination polymers (CPs) [1] and metal–organic frameworks (MOFs) [2] has been a focus in the research community due to their unique features and wide-ranging applications [3–6]. These properties can obtained by appropriate choices of metal ions, ligands, and bridging moieties. One-pot synthesis [7] of the required building blocks is one of the efficient strategies to design such topologies based on strong metal–ligand covalent interactions [8] and multiple weak noncovalent interactions such as hydrogen bonds [9]. First-row transition-metal ions with * Chandan Adhikary [email protected] Habibar Chowdhury [email protected] 1



Department of Chemistry, Kabi Nazrul College, Murarai, Birbhum, West Bengal 731 219, India

2



Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Parco Area delle Scienze 17/A, 43124 Parma, Italy

3

Department of Education, The University of Burdwan, Golapbag, Burdwan, West Bengal 713104, India



different nuclearities and versatile pseudohalide bridges have attracted great interest due to their interesting structure and catalytic and magnetic properties [10–15] and as models for the active sites of biomolecules [16]. Symmetrical and unsymmetrical 1,2-diamine ligands [17] are useful blocks to obtain coordination polymers with diverse dimensionalities. Homoatomic azide ions [18–25] are mostly employed because of their bridging versatility, yielding coordination compounds with a wide range of structural properties and fun