Magnetic properties of a novel quasi-2D Cu(II)-trimer system.

We present structural and magnetic data of a new Cu(2+)(S = 1/2)-containing magnetic trimer system 2b·3CuCl(2)·2H(2)O (b = betaine, C(5)H(11)NO(2)). The trimers form a quasi-2D quantum spin system with an unusual intra-layer exchange coupling topology, which, in principle, supports diagonal four-spin exchange. To describe the magnetic properties, a 2D effective interacting-trimer model has been developed including an intra-trimer coupling J and two inter-trimer couplings J(a) and J(b). The low-energy description and effective parameters are obtained from numerical calculations based on four coupled trimers (with periodic boundary conditions). Fits to the experimental data using this model yield the magnetic coupling constants J/k(B) = -15 K and J(a)/k(B) = J(b)/k(B) = -4 K. These parameters describe the susceptibility and magnetization data very well over the whole temperature and field range investigated. Moreover, the model calculations indicate that, for certain ranges of the ratio J(b)/J(a), which might be accessible by either chemical substitution and/or hydrostatic pressure, the low-energy properties of 2b·3CuCl(2)·2H(2)O will be dominated by non-trivial four-spin exchange processes.

Mono-, di-, and oligonuclear complexes of Cu(II) ions and p-hydroquinone ligands: syntheses, electrochemical properties, and magnetic behavior.

Four highly soluble square-planar Cu(II) and Ni(II) complexes of siloxy-salens (2SiCu, 2SiNi) and hydroxy-salens (2Cu, 2Ni) have been synthesized. An X-ray crystal structure analysis was performed on 2SiCu, 2SiNi, and 2Ni. The compounds have been investigated by cyclic voltammetry, UV-vis-NIR spectroelectrochemistry, and EPR spectroscopy. According to these results, the monooxidized species [2SiCu]+ and [2SiNi]+ are to be classified as Robin-Day class II and III systems, respectively. Magnetic measurements on the dinuclear (PMDTA)Cu(II) complex 1Cu2 x (PF6)2 with deprotonated 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)-benzene (1) linker revealed antiferromagnetic coupling between the two Cu(II) ions thereby resulting in an isolated dimer compound. Coordination polymers [1Cu]n(H2O)(2n) of Cu(II) ions and bridging p-hydroquinone linkers were obtained from CuSO4 x 5 H2O and 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)benzene. X-ray crystallography revealed linear chains running along the crystallographic a-direction and stacked along the b-axis. Within these chains, the Cu(II) ions are coordinated by two pyrazolyl nitrogen atoms and two p-hydroquinone oxygen atoms in a square-planar fashion.