Explorations of New Second-Order Nonlinear Optical Materials in the Ternary Rubidium Iodate System: Noncentrosymmetric β‑RbIO<sub>3</sub>(HIO<sub>3</sub>)<sub>2</sub> and Centrosymmetric Rb<sub>3</sub>(IO<sub>3</sub>)<sub>3</sub>(I<sub>2</sub>O<sub>5</sub>)(HIO<sub>3</sub>)<sub>4</sub>(H<sub>2</sub
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Two new rubidium iodates, namely, β-RbIO3(HIO3)2 (1, P1) and Rb3(IO3)3(I2O5)(HIO3)4(H2O) (2, P21/c), have been synthesized by hydrothermal reaction and their structures determined by single-crystal X-ray diffraction. Compound 1 exhibits IO3– anions and neutral HIO3 molecules which are interconnected by Rb+ cations into three-dimensional structure. Compound 2 features a two-dimensional layered structure formed by IO3– anions and neutral HIO3 and dimeric I2O5 molecules interconnected by Rb+ cations. Large bulk crystal of 1 with dimensions of several millimeters has been grown. UV–vis–NIR transmission spectroscopy measurements on a slab of a polished crystal of 1 indicated that the crystal possesses a short-wavelength absorption edge onset at 305 nm. Powder second-harmonic generation (SHG) measurements on sieved crystals revealed that 1 is a type I phase-matchable material with an SHG response about 1.5 times that of KH2PO4. The Vickers hardness of crystal of 1 has been measured to be 110 HV, and the laser-induced damage threshold has been confirmed to be 18.26 J/cm2 with a laser wavelength of 1064 nm and a pulse duration of 10 ns. Moreover, thermal stabilities and vibrational spectra for both 1 and 2 have also been studied.
