Syntheses And Characterizations Of Series Of Inorganic And Organic Bride Compounds Based Upon Broate Units

Boron coordinate with oxygen not only in triangular BO3but also in tetrahedral BO4.These BO3and BO4groups may further link together via common oxygen atoms to form isolated rings and cages or polymerize into infinite chains, sheets and networks, which result in the compound ity of the structures of borates. Borate materials have long been a focus of research for their variety of structure types and potential applications in magnetic, luminescence and nonlinear optical materials.In this thesis, three new rare-earth polyborates, six alkali-metal polyborates, two new organic borates, one new organic-inorganic hybrid borates and five new adducts of bis-pyridine and triarylboroxines have been synthesized by hydrothermal(solvothermal) reaction, boric acid’flux’reaction and solution reaction. These compounds have been characterized by a combination of X-ray powder diffraction, FT-IR spectrum, UV spectrum and thermogravimetric analysis as well as single crystal X-ray diffraction studies.Three new rare-earth polyborates with formula Dy2B10O18·H2O (1), Nd[B5O8(OH)]NO3·2H2O (2) and Nd[B4O6(OH)2]Cl·H2O (3) were synthesized by boric acid ’flux’ reaction. The fundamental building block (FBB) of compound1is [B5O10], the FBB shares two common oxygen atoms with the adjacent FBB, producing an infinite borate [B5O9]n chain. The infinite chains are thus interconnected by Dy3+ions to form three-dimensional structure compound. The FBB of compound2is [B5O11], the FBB shares four common oxygen atoms with the adjacent FBB, producing a infinite borate [B5O11]n layer containing eighteen-member ring window. The FBB of compound3is [B4O7(OH)2], the FBB shares three common oxygen atoms with the adjacent FBB, producing an infinite borate [B4O7(OH)2]n layer containing eighteen-member ring.Six alkali-metal polyborates with formula LiB507(OH)2(4), Na2(H2O)8·[B4O5(OH)4](5), Na6[B4O5(OH)4]3·8H2O (6),[Na2(H2O)3][B5O8(OH)2](7), Na(enH2)][B7O10(OH)4](8) and K[B5O6(OH)4]-2H2O (9) have been synthesized by hydrothermal(solvothermal) reaction, boric acid’flux’reaction and solution reaction. The FBB of compound4is [B507(OH)2], the FBB shares two common oxygen atoms with the adjacent FBB, producing an infinite borate chain. Compound5and compound6consists of polyions [B4O5(OH)4]2-and a zigzag chain with composition {Na4(H2O)16}n4n+. The FBB of compound7is [B5O8(OH)2], the FBB are interconnected by Na+ions to form infinite layers structure. The FBB of compound8is [B7O10(OH)4], the FBB are interconnected by Na+ions to form infinite layers structure. The FBB of compound9is [B5O6(OH)4], the FBB are interconnected by K+ions to form infinite layers structure.Three new organic-inorganic hybrid borates with formula (1,10-phen)(H36O3)2(10),[2-EtpyH][B5O6(OH)4](11) and [Mn(dien)2][B5O6(OH)4]2(12) were synthesized by solvothermal reaction.Five new adducts of bis-pyridine and boroxines with formula (B3O3Ph3)(bpy)C6H6(13),(B3O3Ph3)2(bpy)-2C7H8(14),(B3O3Ph3)2(bpy)·2C6H14(15),(B3O3Ph3)2(bpe)·C6H6(16) and (B3O3Ph3)2(bpea)·C7H8(17) were synthesized by the reaction of phenylboronic acid and4,4’-bipyridine(bpy),1,2-bis(4-pyridine)ethylene (bpee),1,2-bis(4-pyridyl)ethane (bpea). The crystal structure of13shows that the bpy ligand is bonded to the boroxine molecule through a B-N bond and a C-H-N hydrogen bond, while14-17show that bis-pyridine ligands are bonded to the boroxine molecule through two B-N bonds.