Rational design of nonlinear optical materials based on 2D coordination networks

Zinc(II) and cadmium(II) coordination networks with m-pyridinecarboxylate bridging ligands, Zn(nicotinate)(2), 1, Cd(nicotinate)(2), 2, Cd{3-[2-(4-pyridyl)ethenyl]benzoate}(2), 3, Zn-4-{3-[2-(4-pyridyl)ethenyl]benzoate}(8).3-[2-(4-pyridyl)ethenyl]benzoic acid}. (H2O), 4, Zn{4-[2(3-pyridyl)ethenyl]benzoate}(2).H2O, 5, and Zn{5-[2-(3-pyridyl)ethenyl]thiophene-2-carboxylate}(2), 6, have been synthesized under hydro(solvo)thermal conditions. With the exception of 5, these compounds adopt 2D grid structures. The use of unsymmetrical bent m-pyridinecarboxylate ligands leads to the formation of intrinsically acentric 2D grids which provide an interesting structural motif for the rational synthesis of polar solids. Compounds 1 and 3 - 5 are non-centrosymmetric and show significant powder second harmonic generation efficiencies. Compound 2 adopts a centrosymmetric structure due to the presence of a mu (2)eta (3)-carboxylate bridge, while compound 6 adopts a centrosymmetric structure due to the presence of 2-fold interpenetration. The present work illustrates the potential of rational synthesis of nonlinear-optical-active acentric solids by exploiting the propensity of the formation of 2D coordination networks based on bent linking groups. Crystal data for 1: tetragonal space group P4(3)2(1)2, a = 7.709(1) Angstrom, b = 7.709(1) Angstrom, c = 20.327 Angstrom, and Z = 8. Crystal data for 2: monoclinic space group P2(1)/n, a = 10.055(1) Angstrom, b = 10.219(1) Angstrom, c = 12.733(1) Angstrom, beta = 105.169(2)degrees, and Z = 4. Crystal data for 3: orthorhombic space group Fdd2, a = 20.622(1) Angstrom, b = 36.426(1) Angstrom c = 6.241(1) Angstrom, and Z = 8. Crystal data for 4: monoclinic space group Cc, a = 21.875(2), b = 15.158(1) Angstrom, c = 32.863(2) Angstrom, beta = 102.997(1), and Z = 4. Crystal data for 5: orthorhombic space group P2(1)2(1)2, a = 7.625(1) Angstrom, b = 25.430(2) Angstrom, c = 5.863(1) Angstrom, and Z = 4. Crystal data for 6: orthorhombic space group Pcca, a = 17.150(2) Angstrom, b 9.966(1) Angstrom, c = 12.108(2) Angstrom, and Z = 8.