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Unexpected Strong Antiferromagnetic Interaction in [CuCyclam][Ni(1,2‐benzenedithiolate) 2 ] 2
Author(s) -
Nishijo Junichi,
Iwama Kazuya,
Enomoto Masaya
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402818
Subject(s) - ferrimagnetism , antiferromagnetism , chemistry , crystallography , stacking , crystal structure , molecule , ion , acetonitrile , magnetic susceptibility , magnetism , stereochemistry , condensed matter physics , magnetization , magnetic field , physics , organic chemistry , chromatography , quantum mechanics
Two new molecule‐based magnetic materials were prepared, namely, [CuCyclam(CH 3 CN) 2 ][Ni(bdt) 2 ] 2 and [CuCyclam][Ni(bdt) 2 ] 2 (bdt = 1,2‐benzenedithiolate). The former compound is characterized by a two‐dimensional layer structure, in which axially coordinated acetonitrile molecules prevent cation–anion stacking. The weak antiferromagnetic interaction of 2 J / k B = –6.2 K between the adjacent [CuCyclam(CH 3 CN) 2 ] + ( S = 1/2) and [Ni(bdt) 2 ] – ( S = 1/2) moieties leads to a ferrimagnetic transition at 2.6 K. In contrast to the structure of [CuCyclam(CH 3 CN) 2 ][Ni(bdt) 2 ] 2 , the crystal structure of [CuCyclam][Ni(bdt) 2 ] 2 is characterized by alternately stacked [CuCyclam] 2+ and [Ni(bdt) 2 ] – units, and another [Ni(bdt) 2 ] – anion bridges the chain to form a two‐dimensional ferrimagnetic layer. The magnetic susceptibility of [CuCyclam][Ni(bdt) 2 ] 2 reveals a quite strong intrachain antiferromagnetic interaction of 2 J / k B = –66 K between the [CuCyclam] 2+ and [Ni(bdt) 2 ] – ions. The weak interchain and interlayer interactions make the crystals antiferromagnetic below 3.2 K.