Issue 7, 2003
From the journal:

Dalton Transactions

Syntheses, crystal structures, ferroelectrics and magnetic properties of [R-BzPy]2[Cu(mnt)2] complexes ([R-BzPy]+ = 1-(4′-R-benzyl)pyridinium, R = NO2 or Br; mnt2− = maleonitriledithiolate)

Xiaoming Ren,ab   Jing Ma,c   Changsheng Lu,b   Senzu Yang,*a   Qingjin Meng*b  and  Peiheng Wu*a  

* Corresponding authors

a Department of Electronic Science & Engineering, Nanjing University, Nanjing, P. R. China

b Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, P. R. China

c Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing, P. R. China

Abstract

The structures of two ion-pair complexes, which consist of 1-(4′-R-benzyl)pyridinium (R = NO2 (1), Br (2)) and bis(maleonitriledithiolato)cuprate(II), have been determined by X-ray single crystal analyses, and the results show the stacking patterns in 1 and 2 are different from each other although the difference between the molecular structures of these complexes is only the substituent of the benzene ring, which may arise from the difference of interactions between cations and anions in these two complexes. Complex 1 crystallizes in the non-centrosymmetric space group P1, and dielectric measurements shows ferroelectric behavior with a small hysteresis loop. Quantum chemistry calculation further indicate the electric dipole in a unit cell is 56.5509 Debye, and DSC analysis reveal a Tc of 377 K, from the paraelectric to the ferroelectric phase. The magnetic susceptibilities of these two complexes measured in the temperature range 1.8–260 K show an antiferromagnetic coupling feature between neighboring Cu(II) ions with θ = −0.580 K for 1 and −2.167 K for 2. The polycrystalline EPR spectra of the two complexes at room temperature are different from each other, characterized axial g tensors are g‖ of 2.09, g⊥ of 2.02 for 1, and g‖ = 2.05, g⊥ = 2.03, A‖ = 40.6 × 10−4 cm−1 for 2.

Graphical abstract: Syntheses, crystal structures, ferroelectrics and magnetic properties of [R-BzPy]2[Cu(mnt)2] complexes ([R-BzPy]+ = 1-(4′-R-benzyl)pyridinium, R = NO2 or Br; mnt2− = maleonitriledithiolate)

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Article information

DOI
https://doi.org/10.1039/B210314A
Article type
Paper
Submitted
21 Oct 2002
Accepted
14 Feb 2003
First published
24 Feb 2003

Dalton Trans., 2003, 1345-1351

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Syntheses, crystal structures, ferroelectrics and magnetic properties of [R-BzPy]2[Cu(mnt)2] complexes ([R-BzPy]+ = 1-(4′-R-benzyl)pyridinium, R = NO2 or Br; mnt2− = maleonitriledithiolate)

X. Ren, J. Ma, C. Lu, S. Yang, Q. Meng and P. Wu, Dalton Trans., 2003, 1345 DOI: 10.1039/B210314A

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