Substituent group tuned tri- and binuclear porphyrin-based cyanide-bridged bimetallic complexes: synthesis, crystal structures and magnetic properties

作者：Zhang, Daopeng^*; Zhao, Zengdian; Wang, Ping; Ni, Zhonghai

来源：CrystEngComm, 2013, 15(13): 2504-2511.

DOI：10.1039/c3ce27064e

• SINGLE-MOLECULE MAGNETS
• SPIN-CROSSOVER BEHAVIOR
• ELECTRON-TRANSFER
• CHAIN
• FE
• MN
• CLUSTERS
• CO
• TRANSITION
• METALATION

A series of six cyanide-bridged heterobimetallic complexes including {[M(L)(2)](2)[Mn(TPP)]}[Mn(TPP)(MeOH)(2)]center dot xH(2)O center dot yMeOH {L = 1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate (bpb(2-)), M = Cr (1), Co (2); L = 1,2-bis(pyridine-2-carboxamido)benzenate (bpmb(2-)), M = Cr (3), Co (4); TPP = meso-tetra(phenyl) porphyrin} and {[M(bpb)(CN)(2)][Mn(TClPP)(MeOH)]}center dot xH(2)O center dot yMeOH {M = Cr (5), Co (6), TClPP = meso-tetra(4-chlorophenyl)porphyrin} were designed and synthesized with two manganese(III)-porphyrin compounds and four pyridinecarboxamide dicyanidemetalates as building blocks. X-ray diffraction analysis reveals that compounds 1-4 containing the [Mn(TPP)](+) ion connect two dicyanide-containing [M(L)(CN)(2)](-) anions to form the anionic trinuclear sandwich-like M-III-Mn-III-M-III molecular moiety with the one [Mn(TPP)(CH3OH)(2)](+) segment as a balance cation. The M-III-Mn-III complexes 5 and 6 show a dinuclear molecular conformation comprised of [M(bpb)(CN)(2)](-) and [Mn(TClPP)(MeOH)](+) ions bridged by one cyanide group linking the Mn-III ion. Investigation of magnetic properties of the cyanide-bridged Cr-Mn complexes reveals the weak antiferromagnetic interaction between Mn-III and Cr-III magnetic centers with J(MnCr) = 20.116(2), 20.092(2) and 20.86(2) cm(-1) for 1, 3, and 5, respectively.

• 出版日期2013
• 单位中国矿业大学（北京）; 山东理工大学; 北京科技大学