Synthesis And Characterization Of Borates Supported By Metal-organic Complexes

Borate with abundant structure diversities are of tremendous interest over the years due to their myriad promising applications.Such as nonlinear optics（NLO）,mineralogy and fluominescence.Besides,with the rising of the research on metal-organic complexes,it brings a new research route to obtain novel compounds.Under hydro/solvothermal condition,transition-metal complexes（TMcs）can not only act as templates to regulate the formation of frameworks,but also combinate with low-dimensional substructures into diverse extended frameworks.Moreover,the nature of metal-organic complex can modify electronic,optical,and magnetic properties in borates.Great efforts have been made by our group in exploring novel borates template by different organic agents and transition-metal complexes.Ethylamine,1,3-diaminopropane（1,3-dap,dap）and 1,4-butanediamine（1,4-dab,dab）were used and heteroatoms such as Al/Co/Zn/Cd were introduced during the study.As a continued work,series of compounds have been synthetized and characterized by powder X-ray diffraction,single X-ray diffraction,IR spectra,elemental analysis,UV-VIS,fluorescence spectroscopy and thermogravimetric（TG）analysis.Besides,NLO proterties of those compounds crystalized in acentric space group have been measured.These compounds are categorized into 2 groups as following:1.Aluminoborate templated by organic amine.（H₂dab）[Al B₅O₁₀]（3-1）2.Inorganic-organic hybrid borates supported by metal-organic complexes.[Zn（en）₂][B₇O₁₀（OH）₃]（3-2）[Cd（en）（dab）_0.5][Al B₅O₁₀]（3-3）[Zn（en）（dab）]Zn_0.5[B₅O₈（OH）₂]（3-4）[Zn（dab）][BO（OH）][B₄O₇（OH）]（3-5）[Cd（dab）][BO（OH）][B₄O₇（OH）]（3-6）[Co（dap）][B₄O₉]（3-7）[Zn（dab）₂][Al₂B₁₀O₂₀]（dab）·H₂O（3-8）Compound 3-1 contains a 3-6 open framework templated by 1,4-dab.The NLO property of 3-1 is about 0.9 times that of KDP（KH₂PO₄）.3-2 contains 2D oxoboron layer interconnected by Zn complex via elongated Zn-O bond,which constructing the 3D inorganic-organic hybrid framework.While in 3-3 is a cadmium borate comtaining mixed-amine complex.Cationic‘dumbbell-shaped’transition-metal organic complexes hang in the14-MR windows of the anionic 3D aluminoborate framework,leading to the final 3D hybrid structure.While in 3-4 there also exist mixed amine complex.Rare linear Zn₃ trimers construct with mixed-amines forming 1D metal-organic chains,which join together with[B₅O₈（OH）₂]units into 2D layers.3-5,3-6 and 3-7 are a series of 3D framework supported by metal-organic chains.3-5 and 3-6 are consist of 1D oxoboron chains ad supported into 3D hybrid frameworks by metal-organic chains,while 3-7 contains a 3D oxoboron framework with chiral metal-organic chains located in the channels,which leading to the whole chiral framework.3-8 has a unique structure consisting of both 3D aluminoborate framework and3D metal-organic framework,which interpenetrated by each other.The NLO property of 3-8 is 2.4 times that of KDP.