| The boron atoms can coordinate with oxygen not only in four-fold coordination (tetrahedral, BO4) but also in three-fold coordination (triangular, BO3), which leads to the many kinds of borates with complex structures existed and there are the source as functional materials. The nature of gallium is similar to boron, and the gallium atoms can coordinate with oxygen in four, five, six-fold coordination (GaO4, GaO5, GaO6). Since both of the boron and gallium have a very rich coordinated forms, we can expect obtaining microporous compounds built by B-O cluster and Ga-O cluster. In this thesis, we have synthesized some alkali borates, organic base borates, gallium phosphates, and the other organic amine templeted microporous crystals under the hydrothermal, solvothermal and ionothermal conditions, and further characterized by chemical analysis, elemental analysis, FT-IR, XRD and TG-DTA. The crystal structures of new compounds have been determined by the single crystal X-ray diffraction. The standard molar enthalpies of formation of some borates have been measured by using a heat conduction microcalorimeter. Fluorescence properties of some obtained compounds have also studied.Eight borates, Li4[B8O13(OH)2]·3H2O, Na6[B4O5(OH)4]3·8H2O, Na2[H2TMED][B7O9(OH)5]2, [Emim][B5O6(OH)4], [Pmim][B5O6(OH)4], [(CH3)3NH][B5O6(OH)4], Na[Mn(H2O)2(BP2O8)]·H2O and K[Mn(H2O)2(BP2O8)]·H2O, have been synthesised under the hydrothermal, solvothermal and ionothermal conditions. The compound Li4[B8O13(OH)2]·3H2O crystallizes in the triclinc space group P1 with unit cell dimensions a=8.4578(5) A,b=8.7877(5) A, c=10.8058(7) A,α=87.740(3)°,β=71.819(3)°,γ=61.569(3)°, V=665.26(7) A3, Z=2, which contains the largest odd ring of boron. The compound Na2[H2TMED][B7O9(OH)5]2 crystallizes in the monoclinc space group P2t/c with unit cell dimensions a=11.6329(2) A,b=11.9246(3) A, c=10.2528(2) A,,β=100.178(2)°,V=1399.86(5) A3,Z=4, which is the first example of heptaborate co-templated by alkali metal and organic base. The compound Na6[B4O5(OH)4]3·8H2O crystallizes in the trigonal space group R32 with unit cell dimensions a=11.153(12) A,b=11.153(12) A, c=21.22(2) A,γ=120°, V=2286(4) A3, Z=3. All of the [Emim][B5O6(OH)4], [Pmim][B5O6(OH)4] and [(CH3)3NH][B5O6(OH)4] crystallize in the monoclinc space group P21/c, the unit cell dimensions a=9.4239(4) A,b=15.3927(9) A, c=10.4799(5) A,β=91.634(4)°,V=1519.59(13) A3, Z=4 for [Emim][B5O6(OH)4]; a=9.5108(17) A,b=15.659(3) A, c=10.356(2) A,β=90.367(3)°, V=1542.2(5) A3,Z=4 for [Pmim][B5O6(OH)4]; a=9.3693(11) A, b=14.0375(17) A, c=10.0495(9) A,β=91.815(9)°, V=1321.1(3) A3, Z=4 for [(CH3)3NH][B5O6(OH)4]. The [B5O6(OH)5]- groups are held together through a hydrogen-bond system (O-H…O) forming a three-dimensional structure with channels, between which the organic base cations are intercalated to compensate the negative charges and interact with the [B5O6(OH)5]- anion both electrostatically and via hydrogen bonds of N-H…O. Both of the Na[Mn(H2O)2(BP2O8)]·H2O and K[Mn(H2O)2(BP208)]·H2O crystallize in the hexagonal space group P6522. The unit cell dimensions a=9.6413(9) A, b=9.6413(9) A, c=16.0389(15) A,γ=120°, V=1291.1(2) A3, Z=6 for Na[Mn(H2O)2(BP2O8)]·H2O; a=9.683(4) A, b=9.683(4) A, c=l6.139(6) A,γ=120°, V=1310.5(9) A3, Z=6 for K[Mn(H2O)2(BP2O8)]·H2O. The unit of polyanion [Mn(H2O)2(BP2O8)]- with neighboring units sharing oxygen atoms and forming a three-dimensional open structure with channels.Three novel gallium phosphate compounds, K[MnGa2(PO4)3(H2O)2], K0.5Rb0.5[MnGa2(PO4)3(H2O)2] and Cs[MnGa2(PO4)3(H2O)2] have been synthesised under hydrothermal and solvothermal conditions. All of them crystallize in the monoclinc space group C2/c. The unit cell dimensions a=13.5336(11) A, b=10.1792(10) A, c=8.8703(7)A,β=107.9480(10)°, V=1162.52(17) A3, Z=4 for K[MnGa2(PO4)3(H2O)2]; a=13.5504(12) A, b=10.2965(9) A, c=8.9072(8) A,β=108.53(0)°, V=1178.34(18) A3, Z=4 for K0.5Rb0.5[MnGa2(PO4)3(H2O)2]; a=13.482(5) A, b=10.407(3) A, c=8.913(3) A,β=109.125(5)°, F=1181.6(7) A3, Z=4 for Cs[MnGa2(PO4)3(H2O)2]. The anion [MnGa2(PO4)3(H2O)2]- units are connected together through the common oxygen atoms shared by both gallium and phosphorus atoms to neighboring units forming a 3D open framework with 8-membered ring channels along the c axis, in which the alkali cations are located to compensate the negative charges and interact with the polyanion framework electrostatically.Three novel organic amine templated microporous compounds, (C2N2H10)[Co(PO4)]2, Li(C2N2H10)[In2(HPO4)3(PO4)] and (C4H15N3)[Ga3P3O12F2] have been synthesised under the hydrothermal and solvothermal conditions. The compound (C2N2H10)[Co(PO4)]2 crystallizes in the tetragonal space group P42/n with unit cell dimensions a=10.4619(12) A, b=10.4619(12) A c=9.006(2) A,γ=90°, V=985.8(3) A3, Z=4; The compound Li(C2N2H10)[In2(HPO4)3(PO4)] crystallizes in the monocline space group Pccn with unit cell dimensions a=9.4692(13) A b=9.1622(12) A, c=9.7063(14) A,β=117.5620(10)°, V=746.54(18) A3, Z=2. The compound (C4H15N3)[Ga3P3O12F2] crystallizes in the orthorombic space group Pbca with unit cell dimensions a=16.0206(19) A, b=10.1070(12) A, c=18.533(2) A,α=90°, V=3000.9(6) A3, Z=8. All of them are of microporous structures templated by organic amines, and the polyanion [In2(HPO4)3(PO4)]3- is the novel indium phosphate anion.The molar enthalpies of solution ofβ-Li3B5O8(OH)2, Li4[B8O13(OH)2]·3H2O, Na6[B4O5(OH)4]3·8H2O, K4[B10O15(OH)4] and Cs2B7O9(OH)5, in 1 mol·L-1 HCl(aq) have been determined by microcalorimeter at the 298.15 K, respectively. With the incorporation of the previously determined enthalpies of solution, together with the use of the standard molar enthalpies of formation for LiCl·H2O(s), NaCl(s), KCl(s), CsCl(s), H3BO3(s), HCl(aq) and H2O(1), the standard molar enthalpies of formation of these borates were obtained on the basis of the appropriate thermochemical cycles.The photoluminescence properties of the synthetic samples ofβ-Li3B5O8(OH)2, Na6[B4O5(OH)4]3·8H20, K4[B10O15(OH)4], [Pmim]B5O6(OH)4], Na2[H2TMED][B7O9(OH)5]2, K[Mn(H2O)2(BP2O8)]·H2O, Li(C2N2H10)[In2(HPO4)3(PO4)] and (C4H,5N,)[Ga3P3O12F2] in the solid state at room temperature were investigated by fluorescence spectrophotometer.The research results of this thesis enrich the contents of borate and gallium phosphate chemistry, which are of significance to the exploitation of functional borates and gallium phosphates microporous material.
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