Syntheses, Crystal Structures, and Magnetic Properties of Two Cyano‐Bridged Cr^IIIM^II (M = Cu, Ni) Bimetallic Assemblies with Macrocyclic Ligands

Abstract

Two new cyano-bridged molecule-based magnets, [(CuL 4 ) 2 {Cr(CN) 6 } 2 ] n ·n[Cu(H 2 O) 2 L 4 ]·4nCH 3 OH·2nH 2 O(1) (L 4 = 3,10-dibutyl-1,3,5,8,10,12-hexaazacyclotetradecane) and [(NiL 3 ) 3 {Cr(CN) 6 } 2 ] n ·6nH 2 O (2) (L 3 = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane), have been prepared by self-assembly of [Cr(CN) 6 ] 3and [M(macrocycle)] 2+ (M = Cu, Ni) building blocks and characterized by elemental analysis, IR spectroscopy, thermoanalysis, single-crystal Xray structure analysis and magnetic measurements. The structure of 1 mainly consists of cyanide-bridged Cr III -Cu II 1D anionic chains of [(CuL 4 ) 2 {Cr(CN) 6 } 2 ] n 2n-, in which each[a]

Crystal structure oftrans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ4N3,N6,N10,N13)bis(5-methyltetrazolato-κN)nickel(II) from synchrotron data

“…A search of the Cambridge Structural Database (Version 5.35, May 2014 with 3 updates; Groom & Allen, 2014) indicated that 71 Ni II azamacrocyclic complexes with alkyl pendant groups have been reported. These complexes with various alkyl pendant groups were investigated as good building blocks for supramolecular chemistry and also studied for their magnetic properties and gas sorption abilities due to the anions such as cyanido groups and carboxylic acid derivatives (Hyun et al, 2013;Shen et al, 2012). No corresponding Ni II azamacrocyclic complex with a butyl pendant group and tetrazole derivatives has been reported, and the title compound was newly synthesized for this research.…”

Crystal structure oftrans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ4N3,N6,N10,N13)bis(thiocyanato-κN)nickel(II) from synchrotron data

“…In particular, Ni II macrocyclic complexes having vacant sites in the axial positions have been used for the synthesis of new supramolecular materials with interesting properties, including chiral recognition (Ryoo et al, 2010) and gas storage (Suh et al, 2012). For example, Ni II complexes with alkyl-substituted tetra-azamacrocyclic ligands and anionic tetrazole derivatives, metal cyanide and azide (Shen et al, 2012;Kim et al, 2015) have been studied as magnetic materials and substrates for crystal engineering. The thiocyanate ion is a versatile anionic ligand which can easily bind to a transition metal ion as a terminal or bridging ligand through the nitrogen and/or the sulfur atoms, thus allowing the assembly of multidimensional compounds or heterometallic complexes (Safarifard & Morsali, 2012;Wang & Wang, 2015).…”

Three Chiral Cyanide-Bridged Cr–Cu Complexes: Synthesis, Crystal Structures and Magnetic Properties

“…[17][18][19][20] Compared with the cyanide-bridged heterometallic Fe III -M (M = Cu(II), Ni(II), Mn(II), Mn(III), et al) complexes, [21][22][23][24][25][26][27] the cyanide-bridged heterometallic Cr III -M complexes are still limited due to the shortage of stable and suitable cyanidochromate(III) building blocks. [28][29][30][31][32] In recent years, in order to clearly clarify the magnetic structure correlation in low-dimensional magnetic systems and to prepare interesting low-dimensional molecular magnetic materials, a series of cyanide precursors containing the larger equatorial in-plane ligands and two trans-cyanide groups have been designed. [33][34][35][36][37][38] Studies have shown that these types of cyanide-containing precursors were good choices for assembling cyanide bridged bimetallic magnetic complexes with different structures, such as multinuclear, nanomolecular and one-dimension-al chains, and interesting magnetic properties.…”