Cl-35 NQR study of lattice dynamic and magnetic property of a crystalline coordination polymer {CuCA(phz)(H2O)2}n

Copper(II) compounds {CuCA(phz)(H2O)2}n (H2CA = chloranilic acid, phz = phenazine) having a layer structure of -CuCA(H2O)2- polymer chains and phenazine was studied by 35Cl nuclear quadrupole resonance (NQR). The single NQR line observed at 35.635 MHz at 261.5 K increased to 35.918 MHz at 4.2 K. The degree of reduction of electric field gradient due to lattice vibrations was similar to that of chloranilic acid crystal. Temperature dependence of spin-lattice relaxation time, T1, of the 35Cl NQR signal below 20 K, between 20 and 210 K, and above 210 K, was explained by 1) a decrease of effective electron-spin density caused by antiferromagnetic interaction, 2) a magnetic interaction between Cl nuclear-spin and electron-spins on paramagnetic Cu(II) ions, and 3) an increasing contribution from reorientation of ligand molecules, respectively. The electron spin-exchange parameter |J| between the neighboring Cu(II) electrons was estimated to be 0.33 cm−1 from the T1 value of the range 20−210 K. Comparing this value with that of J = −1.84 cm−1 estimated from the magnetic susceptibility, it is suggested that the magnetic dipolar 2 coupling with the electron spins on Cu(II) ions must be the principal mechanism for the 35Cl NQR spin-lattice relaxation of {CuCA(phz)(H2O)2}n but a delocalization of electron spin over the chloranilate ligand have to be taken into account.