TY - JOUR
T1 - Two polymorphs of (anilinium)(18-crown-6)[Ni(dmit)2]
T2 - Structure and magnetic properties
AU - Nishihara, Sadafumi
AU - Akutagawa, Tomoyuki
AU - Hasegawa, Tatsuo
AU - Fujiyama, Shigeki
AU - Nakamura, Toshikazu
AU - Nakamura, Takayoshi
N1 - Funding Information:
The authors thank Dr. K. Ichimura and Prof. K. Nomura for the use of the SQUID magnetometer. This work was partly supported by a Grant-in-Aid for Science Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan and by the Proposal-Based New Industry Creative Type Technology R&D Promotion Program from the New Energy and Industrial Technology Development Organization (NEDO) in Japan.
PY - 2002/11/1
Y1 - 2002/11/1
N2 - Two polymorphs of monovalent [Ni(dmit)2]- (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)2], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)2]- molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)2], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ = 190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)2]- dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)2]- arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K.
AB - Two polymorphs of monovalent [Ni(dmit)2]- (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)2], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)2]- molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)2], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ = 190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)2]- dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)2]- arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K.
KW - 18-crown-6
KW - Crystal structure
KW - Magnetic properties
KW - Polymorph
KW - Spin ladder
KW - Supramolecular cation
KW - [Ni(dmit)]
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U2 - 10.1006/jssc.2002.9764
DO - 10.1006/jssc.2002.9764
M3 - Article
AN - SCOPUS:0036869987
SN - 0022-4596
VL - 168
SP - 661
EP - 667
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
IS - 2
ER -