Three ion-pair complexes containing bis(maleonitriledithiolate)copper(II) anion and substituted 4-dimethylaminopyridinium: Syntheses, crystal structures, and magnetic properties

作者：Huang Qian; Lin Jing Hua; Liang Li Bo; Chen Xing; Zuo Hong Rong; Zhou Jia Rong; Yang Le Min; Ni Chun Lin^*; Hu Xue Lei

来源：Inorganica Chimica Acta, 2010, 363(11): 2546-2552.

DOI：10.1016/j.ica.2010.04.029

• Substituted 4-dimethylaminopyridinium
• Bis(maleonitriledithiolato) copper(II)
• Crystal structure
• Weak interactions
• Magnetic properties

Three new ion-pair complexes, [4RBzDMAP](2)[Cu(mnt)(2)] (mnt(2) = maleonitriledithiolate; [4RBzDMAP](+) = 1-(4'-R-benzyl)-4-dimethylaminopyridinium, R = F(1), Cl(2) and Br(3)) were synthesized and characterized by elemental analyses, IR, UV, single crystal X-ray diffraction and magnetic measurements. The [Cu(mnt)(2)](2) anions and the cations stack alternately and form a 1D column via C-H center dot center dot center dot S, C-H center dot center dot center dot pi or C-H center dot center dot center dot Cu interactions for 1 and 2. While the cations stack into a column though pi center dot center dot center dot pi or C-H center dot center dot center dot pi interactions between pyridine and phenyl rings for 1 and 3. The change of the molecular topology of the counteraction when the 4-substituted group in the benzyl ring have been changed from F or Cl to Br atom, results in the difference in the crystal system, space group and the stacking mode of the cations and anions of 1, 2 and 3. Some weak hydrogen bonds between the adjacent columns further generate a 3D network structure. It is interesting that 1 and 2 exhibits antiferromagnetic coupling with theta = -2.372 K and theta = -14.732 K, while 3 shows weak ferromagnetic coupling feature with theta = 0.381 K.

• 单位
  华南农业大学