Templated Synthesis, Structure And Characterization Of Borates With Open Framework

Open-Framework borates are an important family of multi-functional materials becauseof their rich structural chemistry and wide applications in mineralogy, semiconductor andoptical fields. In this work, Boric and aluminum which possess flexible coordination ascentric atoms were introduced into the framework of borate. Series of open-frameworkborates were synthesized under hydro(solvo)-thermal and boric flux reaction conditions. Theyare templated by different organic amines, inorganic ion, TM-complex andalkali(earth)-transition metal.Organic amine borates. Six open-framework borates templated by organic amine weresynthesized under solvothermal conditions.[CH3NH2CH3][B5O6(OH)4](3-1,0D)[H2en][B5O8(OH)](en=ethylenediamine,3-2,2D)[CH3CH(CH3)CH2NH3][B5O6(OH)4](3-3,0D)[H2dap]2[B14O20(OH)6](dap=1,3-propanediamine,3-4,0D)[H2dah]2[B14O20(OH)6](dah=1,6-diaminlhexane,3-5,0D)[(H2aep)2][B14O20(OH)6](aep=N-aminoethylpiperazine,3-6,0D)The fundamental building blocks (FBBs) of3-1,3-2and3-3are B5O10clusters,3-1and3-3are isolated structures, the B5O10clusters are linked by extensive hydrogen bonds to form3D supramolecular frameworks.3-2has2D framework with9-MR channels. The structure of3-4,3-5and3-6contain the large isolated [B14O20(OH)6]4-cluster anions. The[B14O20(OH)6]4-anions are linked each other by extensive hydrogen bonds to form a3Dnetwork.Main group metal aluminoborates. Organic aluminum isopropoxide (Al(i-pro)3) which isnot traditional inorganic aluminum sources as aluminum source was introduced into borates.Al(i-pro)3is usually hydrolyzed to chiral AlO4. The synergistic combination between chiralAlO4groups and different acentric B-O clusters produce new acentric aluminoborates. Basedon the above Seven open-framework aluminoborates templated by inorganic ion, organicamine and chiral metal complexes (CMCs) were synthesized under hydro(solvo)thermalconditions. Rb2[AlB5O10]·4H2O (4-1,3D)[C5N2H16][AlB5O10](4-2,3D)[(H2dap)][(CH3)2NH][AlB5O10](4-3,3D)[H2dap][Al(B5O10)](4–4,3D)[(H3aep)][AlB10O16(OH)4]·4H2O (4-5,2D)[(H2aep)2][Al2B11O20(OH)3]·4H2O (4-6,2D)[Zn(1,3-dap)2][AlB5O10](4-7,3D)4-1crystallized in an acentric structure and is templated by inorganic ion. The structurepossess three pairs of8-and6-MR helical channels, odd11-MR channels and showingmoderate SHG signal that is about2.0times the value of KDP.4-2is templated by an organicamine. The framework of4-1is similar to4-2.4-3is co-templated by two types of organicamines containing8-,11-and intersecting14-MR channels.4-4is templated by an organicamine containing9-and10-MR boron ring and exhibiting SHG efficiency about2.0times ofKDP.4-5and4-6using the same organic amine as template.4-5has large16-MR andinteresting chiral8-MR channels.4-6owns double-layer structure containing intersecting10-and11-MR channels.4-7is a new inorganic-organic hybrid solid, containing2Dmetal-organic coordination polymers and the structural features of3D open-frameworkinorganic solids. The3D aluminoborate interpenetrated by2D zinc-amine coordinationpolymer networks. It’s believed that this synthetic approach will offer exciting opportunitiesto create new crystalline hybrid materials with diverse structures and interesting properties.Metal borate. Three extended frameworks alkali (earth) metal, transition metal borateswere made by boric acid flux reaction and solvothermal conditions.Mg2[B5O8(OH)]2·[B(OH)3] H2O (5-1,2D)LiCd3[B9O17]·[B(OH)3](5-2,3D)Li[NH2(CH3)2][B17O26(OH)4](5-3,1D)5-1is an alkali earth metal borate with9-MR channels in2D layers. Then the2D sheetsare held together via the hydrogen bonds interactions resulting in3D supramolecularframework.5-2is3D open framework co-templated by two types of metal. The building unitof5-2is a rare nonaborate group B9O17. The B9O17clusters being SBUs link to each other viaO atoms to form a novel open framework with12-MR channels. The metal cations andneutral borate are housed in16-MR channels. Compound5-3possesses of1D chain with a large curve and is made up of two types of clusters: B12O16(OH)4and B5O10. The alternatingconnection of the B12O16(OH)4and B5O10clusters through O bridges leads to a novel1Dchains.In summary, series of open-framework including organic amine borates, main groupmetal aluminoborates and metal borates, were made under hydro(solvo)thermal conditions orby boric acid flux reaction.They are introduced or selected different types of templates. Thesecompounds were characterized by single crystal X-ray diffraction, X-ray powder diffraction,infrared spectroscopy, ultraviolet spectroscopy and thermo-gravimetric analyzer. Theluminescence and SHG efficiency of some compounds were investigated. The UV-Vis diffusereflectance spectra indicate that most of them are wide-band-gap semiconductors What ismore, most of them have the blue luminescence properties showing they are potential bluelight materials.