Self-assembly of porous two-dimensional copper(II) alpha, beta-unsaturatedcarboxylate complexes with trimethyl phosphate

A new type of two-dimensional network was found in the hydrogen-bonded mole cular assemblies of copper(II) alpha,beta-unsaturated carboxylate complexes with TMP [OP(OMe)(3)], {Cu(2)A(4)(H2O)(2)[OP(OMe)(3)]}(n) [(1) A = CH2=CHC O2-; (2) A = CH2=C(Me)CO2-]. The crystal structure of (1) has been determin ed by single-crystal X-ray diffraction. Both complexes are unique in terms of a sheet structure brought about by OH ... O hydrogen-bonded interactions both between neighbouring Cu(2)A(4)(H2O)(2) units and between Cu(2)A(4)(H2 O)(2) and OP(OMe)(3) molecules. The electronic reflectance spectra in the s olid state suggest a square pyramidal coordination environment around the c opper(II) atom. Room temperature X-band e.s.r. spectra of powered samples a nd variable-temperature magnetic susceptibility studies indicate the presen ce of strong antiferromagnetic exchange interactions between two copper(II) atoms, with 2J = -310 cm(-1) for (1) and 2J = -304 cm(-1) for (2) respecti vely.