Abstract
Crystalline KTiOPO4 (KTP), an inorganic nonlinear optical material with a waveguide figure-of-merit that is twice that of other mixed-metal oxides, contains helical chains of TiO(4/2)O(2/2) octahedra in which a long, short Ti-O bond motif results in a net c-directed polarization. The alternating long and short Ti-O bonds that occur along these chains are the major contributors to the large nonlinear optic and electrooptic coefficients. Analogous chains have been constructed using dichromate [Cr2O7]2- anions and [M(py)4]2+ (M = Cu, Zn) cations; these new transition metal oxides crystallize in the same space group as KTP. Crystal data for Cu(py)4Cr2O7: orthorhombic, space group Pna2(1) (No. 33), with a = 15.941(7) A, b = 16.324(3) A, c = 8.857(2) A, and Z = 4; for Zn(py)4Cr2O7, orthorhombic, space group Pna2(1) (No. 33), with a = 16.503(1) A, b = 16.005(1) A, c = 8.8130(5) A, and Z = 4; for Cd(py)4Cr2O7, monoclinic, space group C2/c (No. 15), with a = 14.8034(9) A, b = 11.1847(7) A, c = 15.788(1) A, beta = 110.023(1) degrees, and Z = 4.
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