Issue 9, 2001
From the journal:

Journal of Materials Chemistry

Tomoyuki Akutagawa,*abc   Nobuhiro Takamatsu,b   Kozo Shitagami,b   Tatsuo Hasegawa,ab   Takayoshi Nakamura,*ab   Tamotsu Inabe,d   Wataru Fujitae  and  Kunio Awagace  

* Corresponding authors

a Research Institute for Electronic Science, Hokkaido University, Sapporo, Japan
E-mail: takuta@imd.es.hokudai.ac.jp
Fax: +81-11-706-4972
Tel: +81-11-706-2884

b Graduate School of Environmental Earth Science, Hokkaido University, Sapporo, Japan

c PRESTO, Japan Science and Technology Corporation (JST), Japan

d Graduate School of Science, Hokkaido University, Sapporo, Japan

e Graduate School of Arts and Science, The University of Tokyo, Meguro, Japan

Abstract

Calcium ion (Ca2+) and crown ethers, 12-crown-4, 15-crown-5, 1-aza-18-crown-6 (A18-crown-6) and 1,10-diaza-18-crown-6 (DA18-crown-6), were assembled into divalent supramolecular cation (SC2+) structures in the monovalent [Ni(dmit)2]− salts (dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolate), which regulate the arrangement of the [Ni(dmit)2]− anions in the crystal. The divalent SC2+–[Ni(dmit)2]− system showed a larger diversity of crystal structures compared with the monovalent SC+ system. Peculiar magnetic behavior was observed depending on the arrangement of the S = ½ spins on the [Ni(dmit)2]− anions. Single crystals of Ca2+(12-crown-4)2[Ni(dmit)2]2 (1) and Ca2+(15-crown-5)2[Ni(dmit)2]2(CH3CN)0.7 (2) had a typical sandwich-type Ca2+(crown ether)2 structure, which included the formation of π–π dimers and monomers of [Ni(dmit)2]− anions in the crystal. The temperature-dependent magnetic susceptibility (χm) of salt 1 showed a magnetic transition at 190 K, at which temperature the spins on each [Ni(dmit)2]− dimer formed a singlet pair. On the other hand, the magnetic behavior of salt 2 obeyed the Curie–Weiss law. The Ca2+ ions in the isostructural single crystals of Ca2+(A18-crown-6)[Ni(dmit)2]2(CH3CN)2 (3) and Ca2+(DA18-crown-6)[Ni(dmit)2]2(CH3CN)2 (4) were completely included into the 18-crown-6 cavity, and further interacted with two CH3CN molecules from the axial position. The resultant Ca2+(18-crown-6)(CH3CN)2 cations induced the formation of uniform zig-zag chains of the [Ni(dmit)2]− anions, the magnetic susceptibility of which were explained by a one-dimensional Heisenberg antiferromagnetic linear chain. The magnetism of these salts was discussed in terms of the intermolecular transfer integral t.

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Article information

DOI
https://doi.org/10.1039/B101873F
Article type
Paper
Submitted
27 Feb 2001
Accepted
02 May 2001
First published
30 May 2001

J. Mater. Chem., 2001,11, 2118-2124

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Diversity in the ½ spin arrangement of [Ni(dmit)2]− anions in divalent Ca2+(crown ether) supramolecular cation salts

T. Akutagawa, N. Takamatsu, K. Shitagami, T. Hasegawa, T. Nakamura, T. Inabe, W. Fujita and K. Awaga, J. Mater. Chem., 2001, 11, 2118 DOI: 10.1039/B101873F

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