Synthesis, Crystal Structure And Properties Of Novle Borates

Inorganic–organic hybrid materials and nonlinear optical materials have attractedconsiderable interest in recent years, due to their novel structures and distinctivephysical–chemical properties. Borate is the largest class of oxide minerals, not only richstructure, but also has important applications in mineralogy, nonlinear optical materials andlaser materials. In order to develop the potential borate materials, fourteen new compoundshave been synthesized on the basis of hydrothermal or solvothermal method in this work.These compounds include inorganic–organic hybrid borates, alkali (–earth) metal boratesand transition–metal borates, which were structurally characterized by IR, UV–Visspectrum and X–ray diffraction analysis. The TG, luminescence and nonlinear opticalproperties of some compounds were investigated.Our group was focused on the synthesis of microporous framework and with NLOproperties borates. Based on these considerations, we get the following types ofcompounds:1. Borates templated by amine and transition–metal complexes[Co(dap)3][B5O6(OH)4]2·H2O (3–1，0D)[Ni(dap)3][B5O6(OH)4]2·H2O (3–2，0D)[Al2B11O20(OH)3](H2aep)2·4H2O (3–3，2D)[Al(B5O10)]·H2dap (3–4，3D)[Al(B5O10)]·H2teta (3–5，3D)[Zn(dap)2][AlB5O10](3–6，3D)Compounds3–1and3–2are isostructural and consist of isolated pentaborate[B5O6(OH)4]–, the anionic groups are linked by extensive hydrogen bonds to form a3Dsupramolecular framework with20–MR large channels.3–3~3–5are aluminoborates byorganic amine, in3–3the aminoethyl piperazine as structure–directing agent, the structurehave2D double layer with11–MR channels. The3–4using1,3–propanediamine astemplate has3D framework, the structure have helical channels and different size channels.Compound3–5have14–MR channels with sra topology.3–6is a new aluminoborate templated by transition–metal complex, which owns8–and11–MR channels, the structureis two–fold interpenetration between anion clusters and transition–metal complex.3–4~3–6have second–harmonic generation (SHG) effect, which are approximately1.2,1.5and0.3times of KDP. The UV–Vis diffuse reflectance spectra indicate that they arewide–band–gap semiconductor materials.2. Alkali metal or alkaline–earth metal boratesLi3[B5O8(OH)2](4–1,2D)Ba[AlB4O8(OH)]·H2O (4–2,2D)Sr2[B6O9(OH)4](4–3,2D)Sr2[B5O9(OH)]·H2O (4–4,3D)The4–1is an alkali metal borate with10–MR channels in2D layers. Compound4–2is an alkaline earth aluminoborate, the structure have2D double layer, the layers are furtherlinked by hydrogen bonding and stacked in–ABAB–fashion to3D network.4–3and4–4are strontium borates,4–3contains chiral layers，4–4is a3D framework, they havesecond–harmonic generation (SHG) effect, which are approximately1.5and2times ofKDP.3. Other metal boratesK6[V12B18O54(OH)6(H2O)](CH3NH3)4·2en·12H2O (5–1，0D)Pb[B5O8(OH)]·H2O (5–2，2D)Pb[B8O11(OH)4](5–3，2D)Zn6O(OH)(BO)3(5–4，3D)Compounds5–1is an inorganic–organic hybrid polyoxovanadoborate, the cage–like[V12B18O54(OH)6(H2O)]10–clusters are connected by hydrogen bonding and K+to rareexample of extended3D framework. The5–2and5–3are layer compounds containingdouble ring or three ring building units, which are share exocyclic oxygen atoms to form9–MR windows, adjacent borate layers are interconnected via ionic Pb–O bonds andhydrogen bonding to form a3D supramolecular network. The5–4is a3D frameworkzincoborate, the Zn–O connected to a rare [Zn6O17] cluster, which is through vertex Oatoms link to2D layer structure, adjacent zinc layers are linked by BO3triangles to3Dframework, this compound have excellent luminescent properties.