Heterometallic Complexes Based on the Mixed Bridging Ligands of Tricyanometalate and Terephthalate: Syntheses, Structures, and Magnetic Properties

Abstract

With the use of the tailored tricyanometalate precursors [(L)Fe(CN)(3)](-) (L = Tp, tris(pyrazolyl)hydroborate; L = i-BuTp, 2-methylpropyltris(pyrazolyl)borate) and terephthalate (ta) units as the mixed bridging ligands, a new one-dimensional (1D) chain polymer {[(Tp)(2)Fe(2)(CN)(6)Cu(2)(ta)(dmbpy)(2)] x 7 H(2)O}(n) (1), a pentanuclear heterometallic cluster [(Tp)(2)Fe(2)(CN)(6)Cu(3)(phen)(3)(ta)(2)(MeOH)(H(2)O)(2)] x 8 H(2)O (2), and a tetranuclear heterometallic cluster [(i-BuTp)(2)Fe(2)(CN)(6)Cu(2)(ta)(phen)(2)(EtOH)(2)] x 2 MeOH x H(2)O (3) (dmbpy = 4,4'-dimethyl-2,2'-bipyridyl, phen = 1,10-phenanthroline) have been synthesized and structurally characterized. The Fe(III) and Cu(II) ions are bridged by cyanides, and the Cu(II) ions are further linked by terephthalate to form the 1D chain polymer, the pentanuclear cluster, and the tetranuclear cluster for complexes 1-3, respectively. All complexes show ferromagnetic interactions between the Fe(III) and Cu(II) ions. Complex 1 shows metamagnetic behavior with the critical field of about 1.2 T at 1.8 K.

Solvothermal in situ synthesis of cyanide-containing ternary silver(I) coordination polymers and their phosphorescent properties

“…[5][6][7][8][9][10] Latterly, the hydro (solvo)thermal synthesis method was adopted, which produces novel homometallic or heterometallic cyanide-containing coordination polymers more efficiently. 3c, [11][12][13][14][15][16] While in both cases cyanometalates are required, serving as cyanide source, the solvothermal in situ generation of CN À from an organonitrile offers a new approach. 17 The CN À is generated either from C-C cleavage reaction of acetonitrile or S-C cleavage of thiocyanate under solvothermal conditions in the presence of metal ions.…”

Syntheses, Structures, and Magnetic Properties of Two Kinds of Unique Heterometallic Chains with Mixed-Bridging Ligands of Tricyanometalate and Alkoxide

“…Though it is difficult to get the individual values of J 1 , J 3 , and J 4 with enough accuracy, the plausible and averaged values of J 1 , J 3 , and J 4 (uniform chain) or J 1 and J 3 (tetranuclear) are close to that of previously reported complexes with bent Fe-CtN-Cu linkage. 34 The |J 2 | value (<10 cm -1 ) in complex 4 is much smaller than that in complexes 1-3, possibly resulting from the distortion of Cu1 ion.…”

Crystal structures and magneto-structural correlation analysis for several cyano-bridged bimetallic complexes based on MnIII–FeIII systems

“…For the cyanometalate building blocks, fac-tricyanidoferrates [Fe III (L)(CN) 3 ] À have been thoroughly investigated. [44][45][46][47][48][49][50] Recently, mer-tricyanidoferrate building blocks such as [Fe III (bpca)(CN) 3 ] À , 51,52 [Fe III (pcq)(CN) 3 ] À , 53 [Fe III (pzcq)(CN) 3 ] À , 54 [Fe III (mpzcq)(CN) 3 ] À , 55 and [Fe III (qcq)(CN) 3 ] À , 56 were designed and employed to construct new low-dimensional complexes. In these relevant complexes, cyano-bridged Mn III -NC-Fe III complexes a School of Chemistry and Chemical Engineering, Jiangsu University, derived from Mn III (Schiff base) and mer-tricyanidoferrate [Fe III (L)(CN) 3 ] À were often of great interest because of their diverse structural modes and their interesting magnetic properties.…”