TY - JOUR
T1 - Flexible cis-cyclohexane-1,4-diammonium ion in magnetic [Ni(dmit) 2] crystals
AU - Ye, Qiong
AU - Shi, Ping Ping
AU - Chen, Zi Qi
AU - Akutagawa, Tomoyuki
AU - Noro, Shin Ichiro
AU - Nakamura, Takayoshi
PY - 2012/8
Y1 - 2012/8
N2 - Reactions exchanging the cation in (nBu4N)[Ni(dmit)2] to cis-cyclohexane-1,4-diammonium (cis-CHDA) in the presence of [18]crown-6, benzo[18]crown-6 (B[18]crown-6) and dibenzo[18]crown-6 (DB[18]crown-6) yielded crystals of the monovalent [Ni(dmit)2] complex, namely (cis-CHDA)([18]crown-6)2[Ni(dmit)2]2 (1), (cis-CHDA)(B[18]crown-6)2[Ni(dmit)2]2 (2) and (cis-CHDA)(DB[18]crown-6)2[Ni(dmit)2]2 (3). The two ammonium groups (-NH3+) of the cis-CHDA dication at axial and equatorial positions interact with oxygen atoms of the corresponding upper and lower crown ethers to form sandwich-type supramolecular cationic structures. The lateral [Ni(dmit)2]- anion arrangements through S-S contacts along the short and long axis of [Ni(dmit)2] anions were realised in crystals of 1, 2, and 3 by the asymmetrical cis-CHDA dication. The temperature- and frequency-dependent anisotropic dielectric constants of a crystal of 1 were evaluated along the a, b and c axes, where the thermally activated motion of the structurally flexible cis-CHDA dication was consistent with the dielectric responses. The motions, dielectric properties and magnetism of [Ni(dmit)2]- salts with flexible cis-cyclohexane-1,4-diammonium ion have been investigated.
AB - Reactions exchanging the cation in (nBu4N)[Ni(dmit)2] to cis-cyclohexane-1,4-diammonium (cis-CHDA) in the presence of [18]crown-6, benzo[18]crown-6 (B[18]crown-6) and dibenzo[18]crown-6 (DB[18]crown-6) yielded crystals of the monovalent [Ni(dmit)2] complex, namely (cis-CHDA)([18]crown-6)2[Ni(dmit)2]2 (1), (cis-CHDA)(B[18]crown-6)2[Ni(dmit)2]2 (2) and (cis-CHDA)(DB[18]crown-6)2[Ni(dmit)2]2 (3). The two ammonium groups (-NH3+) of the cis-CHDA dication at axial and equatorial positions interact with oxygen atoms of the corresponding upper and lower crown ethers to form sandwich-type supramolecular cationic structures. The lateral [Ni(dmit)2]- anion arrangements through S-S contacts along the short and long axis of [Ni(dmit)2] anions were realised in crystals of 1, 2, and 3 by the asymmetrical cis-CHDA dication. The temperature- and frequency-dependent anisotropic dielectric constants of a crystal of 1 were evaluated along the a, b and c axes, where the thermally activated motion of the structurally flexible cis-CHDA dication was consistent with the dielectric responses. The motions, dielectric properties and magnetism of [Ni(dmit)2]- salts with flexible cis-cyclohexane-1,4-diammonium ion have been investigated.
KW - Dielectric anisotropy
KW - Magnetic properties
KW - Molecular motion
KW - Organic-inorganic hybrid composites
KW - Supramolecular chemistry
UR - http://www.scopus.com/inward/record.url?scp=84864658039&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84864658039&partnerID=8YFLogxK
U2 - 10.1002/ejic.201200099
DO - 10.1002/ejic.201200099
M3 - Article
AN - SCOPUS:84864658039
SN - 1434-1948
SP - 3732
EP - 3739
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 23
ER -