1D to 3D Heterobimetallic Complexes Tuned by Cyanide Precursors: Synthesis, Crystal Structures, and Magnetic Properties

作者：Zhang, Daopeng^*; Si, Weijiang; Wang, Ping; Chen, Xia; Jiang, Jianzhuang

来源：Inorganic Chemistry, 2014, 53(7): 3494-3502.

DOI：10.1021/ic4029386

• SINGLE-MOLECULE-MAGNET
• VERSATILE BUILDING-BLOCK
• SPIN-CROSSOVER
• FE-III
• MN-III
• BIMETALLIC ASSEMBLIES
• ORDERING TEMPERATURE
• MIXED-VALENCE
• CHAIN MAGNET
• SCHIFF-BASE

Five new heterobimetallic complexes, namely, {[Ni(L)][Fe(bpb)(CN)(2)]}ClO4 (L = 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene, bpb(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate) (1), ([Ni(L)](3)[M(CN)(6)](2)}center dot 7H(2)O (M = Fe (2), Cr (3)), {[Ni(L)](2)[Mo(CN)(8)]}center dot CH3CN center dot 13H(2)O (4), and {[Ni(L)](2)[W(CN)(8)])center dot 16H(2)O (5), were assembled from the polyaza macrocycle nickel(II) compound and five cyanidometalate precursors containing different numbers of cyanide groups. Single-crystal X-ray diffraction analysis reveals their different structure ranging from a cyanide-bridged cationic polymeric single chain for 1, a two-dimensional network for 2 and 3, and a three-dimensional network for 4 and S. In addition, a systematic investigation over the magnetic properties of 1-3 indicates the ferromagnetic magnetic coupling between neighboring Fe(III)/Cr(III) and Ni(II) ions through the bridging cyanide group. For complex 1, the magnetic susceptibility has been simulated by the Seiden model using the Hamiltonian H = -J Sigma(i=0SiSi+1)-S-N, leading to the magnetic coupling constant of J = 3.67 cm(-1). The two-dimensional magnetic complexes exhibit three-dimensional magnetic ordering behavior with a magnetic phase transition temperature of T-C = 4.0 K for 2 and T-N = 6.0 K for 3, respectively.

• 出版日期2014-4-7
• 单位山东理工大学; 北京科技大学