Two bimetallic W(IV)-Mn(II) complexes based on octacyanometallates: structures and magnetic properties

Abstract

2), have been synthesized and characterized structurally and magnetically. X-ray analysis shows that complex 1 is a one-dimensional (1-D) polymer of W 2 (CN) 4 Mn 2 square units in which adjacent square fragments are interlinked by sharing [W(CN) 8 ] 4− moieties to form an infinite chain. Complex 2 is a three-dimensional (3-D) polymer, which shows an unforeseen structure, exhibiting a 3-D open network with a 1-D channel (ca.13.21 Å × 11.82 Å). Fitting of the magnetic properties indicates that both polymers exhibit weakly antiferromagnetic interactions between the adjacent Mn ions.cyano-bridged, coordination polymer, magnetic property, manganese(Ⅱ) complex

Manganese(II)-Octacyanometallate(V) Bimetallic Ferrimagnets with Tc from 41 to 53 K Obtained in Acidic Media

“…All cyanide groups bridge from W V to Mn II ions giving rise to two coordination environments around Mn II ions. The bond lengths of C−N are 1.121(8), 1.140(11), and 1.114(16) Å, while those of W−C are 2.169(7), 2.176(8), and 2.170(11) Å, respectively, comparable with the reported values. ,− Mn1 has an occupancy rate of 0.75 and accepts 0.75 × 4 cyanide groups by equatorial plane and 0.5 × 2 formate ions and 0.25 × 2 water molecules by the axis directions completing the six-coordinated sphere corresponding to a Mn II ion. In fact, the formate ion is also a bridge between Mn1 and its asymmetrical atoms.…”

“…Up to date, there have been several 3D manganese−octacyanometallate bimetallic complexes reported. For the description, as further below, their structures can be roughly classified as four types by the construction: (i) A typical structure is −[W(CN) 8 ]−Mn 4 −[W(CN) 8 ]−Mn 4 − columnar linkages that share the nodes of Mn II ions and interlock to form the 3D networks, as reported previously; ,, (ii) The well-known [Mn 9 M 6 ] clusters are connected by a bidentate organic ligand to the 3D cluster array; , (iii) The square Mn 2 W 2 units share the nodes of W ions leading to the 3D networks with small pores; ,, and (iv) [W(CN) 8 ] bridges between Mn II ions with N-heterocyclic chelated ligands forming the 3D metal−organic framework. , The structure of complex 1 is different from all the reported complexes, although it crystallizes in tetragonal system similar to those with typical structures. ,, The asymmetrical unit of complex 1 contains an octacyanotungstate(V), 1.75 molecules of manganese(II) with 1.5 molecules of coordinating water and 0.5 molecules of formate ion and one lattice water molecule, in which most atoms are disordered in position leading to a very complicated structure. As shown in Figure a, octacyanotungstate takes a bicapped trigonal prismatic configuration with three disordered cyanide groups occupying four positions of C2N2 and its symmetrical sites.…”

Three interpenetrated copper(II) coordination polymers based on a V-shaped ligand: Synthesis, structures, sorption and magnetic properties

“…The syn,syn carboxlate group mediated antiferromagnetic coupling weaken the ferromagnetic interaction between Cu1 and Cu1B. The long ligands only provided neglectable antiferromagnetic interactions intercluster [30][31][32][33].…”

A three-dimensional cyanide-bridged heterometallic coordination polymer: poly[[diacetonitrilediaqua[μ2-3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine-κ4N1,N6:N3,N4]tetra-μ-cyanido-tetracyanidodimanganese(II)molybdate(IV)] dihydrate]

“…square antiprism (D 4d ), dodecahedron (D 2d ) and bicapped trigonal prism (C 2v )], so that octacyanidometallate-based compounds show rich magnetic properties which range from low-dimensional magnets (SMMs and SCMs) to long-range ordered magnets (Freedman et al, 2006;Herrera et al, 2003;Kashiwagi et al, 2004;Lim et al, 2006;Podgajny et al, 2012;Song et al, 2003Song et al, , 2005Zhong et al, 2000). A variety of structures based on [M(CN) 8 ] 3À/4À , including zero-dimensional clusters, onedimensional chains, two-dimensional networks and threedimenisonal frameworks, have been successfully prepared (Liu et al, 2009;Nowicka et al, 2012). To the best of our knowledge, there are only a few examples based on [Mo(CN) 8 ] 3À/4À and Mn 2+ cations which have been structurally and magnetically characterized so far (Kosaka et al, 2008;Larionova et al, 2004;Le Goff et al, 2004;Ma et al, 2008;Ma & Ren, 2009;Milon et al, 2007;Przychodzeń et al, 2004;Wang et al, 2010Wang et al, , 2014.…”