Polar Compounds Constructed with the [Cr2O7]2- Anion

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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 TiO4/2O2/2 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 Pna21 (No. 33), with a = 15.941(7) Å, b = 16.324(3) Å, c = 8.857(2) Å, and Z = 4; for Zn(py)4Cr2O7, orthorhombic, space group Pna21 (No. 33), with a = 16.503(1) Å, b = 16.005(1) Å, c = 8.8130(5) Å, and Z = 4; for Cd(py)4Cr2O7, monoclinic, space group C2/c (No. 15), with a = 14.8034(9) Å, b = 11.1847(7) Å, c = 15.788(1) Å, β = 110.023(1)°, and Z = 4.

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