Synthesis And Structures Of Inorganic-organic Hybrid Borate, Vanadium Oxide Complexes And Metal Coordination Polymers

The combination of organic molecules with inorganic species may lead toinorganic-organic hybrid materials with special structure features, and organicmolecules can influence the nucleation and growth of inorganic compounds,and control the microstructure in the inorganic frameworks. Throughinteraction between the organic molecules and the inorganic species, theorganic molecules could imprint the structure information to the inorganicframeworks and result in a series of hybrid materials with novel structures andspecial properties. It has proved that inorganic-organic hybrid materials areimportant in the molecule engineering and have potential applications incatalysis, sorption, electrical conductivity, magnetism, photochemistry,biochemistry and medicine.In order to develop the potential application of new kind of inorganic-organicfunctional materials, in this work, the inorganic-organic metal complexes weredesigned and synthesized by hydrothermal and solvothermal technique usingnitrogen-based organic ligand and transition metal as principal part. Thesecomplexes include the borate, vanadium oxide compounds and metalcoordination polymers, and were charactered with the method of CHN, IR,TG-DTA, XRD and X-ray single crystal diffraction. The optical and magneticproperties of some compounds were investigated.Great progress has been made after the borate oxide chemistry wasresearching for about one century, however there are still some challengingfields in structural chemistry and synthetic chemistry of inorganic-organichybrid borate oxide to be further researched.The polyborate anions are existing in the borate crystals. Compounds containanionic components composed of BO3 and BO4 groups that may link togetherby sharing oxygen atoms to form infinite chains, sheets and networks. Usingthe organic amine as structural director and ligand and changing the metalcation, we have successfully synthesize unusual organic-inorganictransition-metal borate species. The structure of the borate compounds, werecharactered with the method of CHN, IR, TG-DTA, XRD and X-ray singlecrystal diffraction. The single crystal structure suggested that the series ofborate complexes have a structure built from chiral metal coordination cations,and two B3O3 rings. The metal cations coordinated to N-atoms of organicamine ligands with different bond lengths and bond angles and formed distortedoctahedral structure. The enantiomer of the metal complex is separated as Δ andΛ configurations in strictly alternate regions. Further investigation of themechanism of forming the chiral metal complex will be of significantimportance. The borate anions existing in the pentaborate are constituted byfour BO3 triangles and one BO4 tetrahedron sharing O atom. In the complex[M(en)3]B5O7(OH)3, extensive O-H···O and N-H···O hydrogen bond exist. Thepentaborate [B5O7(OH)3]2-units in the complexes are arranged as zigzag chainsthrough hydrogen bonding. Hydrogen bond connect polyanions with chiralmetal coordination cations and supermolecular networks are formed. Thephotoluminescence of [Zn(C2N2H8)3]B5O7(OH)3 was determined, its strongemitting peak is at 445 nm. Our work provide a theory for study of thestructures of inorganic-organic hybrid borate single crystals in the future.Many chemists work on the field of vanadium chemistry. Now, many ofinorganic-organic hybrid materials with novel structural have been designedand synthesized, because vanadium has multi-oxidation state and uniquereaction characteristic and coordination configuration.The layered inorganic-organic hybrid vanadium oxide, Mn(C12N2H8)(H2O)V2O6, has been synthesized by hydrothermal technique using transitionmetal and organic amine as structural director and template. Its structure hasbeen characterized by the means of CHN, XRD, IR, TG-DTA and X-ray singlecrystal diffraction. Structure analysis suggests that the compound is a layeredstructure containing two metal oxide layers. In this compound, the inorganicframework sheets are composed of VO4 tetrahedron and MnN2O4 distortedoctahedron. The 3-D supermolecular networks have been formed due to the π -π stacking and the π -π stacking through adjacent phen rings plays animportant role for stability of the crystals. The magnetic analysis reveals thatthere is antiferromagnetic interactions in the compound.Recently, design and assembly of metal coordination polymers containingone dimension, two dimension and three dimension structure has become moreattractive in the research field of chemistry. The metal coordination polymerscontaining imidazole ligand have potential application in material, moleculerecognition and self-assembly due to their optics, magnetism, catalysis andbioactivity.It is difficult to obtain the single crystals because metal coordinationpolymers with bi-dentate imidazole ligand are hard to dissolve into commonorganic solvent. Although these metal coordination polymers have interestingtopological networks, some of them are just determined by X-ray powderdiffraction. It is an important research work to design and synthesize this kindof metal coordination polymers containing novel structure and special functionusing suited ligands and metals.We have synthesized three new metal coordination polymers using two kindof imidazole ligands. The Co(?I), Mn(?I) and Ag(I) were introduced intopolymers by the solvothermal technique and diffuse method. The crystalstructures of [Ag(C8N3H6)]n,, Co(C12N3H10)2(C2H4O2) and Mn(C12N3H10)2(C2H4O2) were characterized by CHN, XRD, IR and X-ray single crystaldiffraction and the photoluminescence spectrum of [Ag(C8N3H6)]n wasobtained. The crystal, [Cu(en)2](CH3COO)2·H2O, was synthesized andcharacterized by X-ray single crystal diffraction during our work.