Boron-containing Inorganic - Organic Hybrid Optical Functional Crystal Materials Synthesis, Characterization And Optical Properties Study

In this paper,12 kinds of inorganic-organic hybrid ammonium and alkali-metallic bis(malic acid)borates have been synthesized by aqueous solution method, and the nonlinear optical properties of these complexes have also been investigated. Five kinds of Lanthanide 2,3-Pyrazinedicarboxylates complexes have been synthesized under hydrothermal conditions, and the fluorescence properties of these complexes have also been investigated. All of these products have been characterized by elemental analysis, IR, TG analysis, XRD and signal-crystal X-ray diffraction analysis. The obtained results are of important significance to the select novel inorganic-organic hybrid light functional crystal materials.(1) Using H3BO3, DL/L-malic acid and MOH as the source materials,12 kinds of ammonium and alkali-metallic bis(malic acid)borates, Li(DL-C8H8BO10)·H2O, Na(DL-C8H8BO10)·H2O, K(DL-C8H8BO10)·H2O, Rb(DL-C8H8BO10)·H2O, Cs(DL-C8H8BO10)·H2O, NH4(DL-C8H8BO10)·H2O, Li(L-C8H8BO10)·H2O, Na(L-C8H8BO10)·H2O, K(L-C8H8BO10)·H2O, Rb(L-C8H8BO10)·H2O, Cs(L-C8H8BO10)·H2O, NH4(L-C8H8BO10)·H2O, have been synthesized by aqueous solution method. In which, the crystal structures of K(C8H8BO10)·H2O and Cs(C8H8BO10)·H2O have been first determined by single crystal X-ray diffraction. The investigation of second-order nonlinear optical properties shows that the Li(DL-C8H8BO10)·H2O,Na(DL-C8H8BO10)·H2O,Rb(DL-C8H8BO10)·H2O,Na(L-C8H8BO10)·H2O,K(L-C8H8BO10)·H2O and NH4(L-C8H8BO10)·H2O have obvious nonlinear multiplier effect, which are near KDP.(2) Five kinds of Lanthanide 2,3-Pyrazinedicarboxylates complexes, (NH4)2[Sm2(pzdc)4(H2O)2], (NH4)2[Gd2(pzdc)4(H2O)2], (NH4)2[Y4(pzdc)2(H2O)2], (NH4)2[Nd2(pzdc)4(H2O)2] and (NH4)2[Er2(pzdc)4(H2O)2] have been synthesized under hydrothermal conditions. The investigation of single crystal X-ray diffraction shows that these complexes are isostructural. In the crystal, [Ln2(pzdc)4(H2O)2]2- units connect each other forming a 3D network structure with channels along the a axis and b axis. The NH4+cations are located in the channels and balance the charge of anion framework. TG analysis shows that these complexes are stable before 300℃. The investigation of luminescent properties of complexes in the solid state shows that the complexes exhibit stronger fluorescence emission of rare earth in the visible region. In addition, such complexes have the ions exchange properties.