| Since the ?A elements such as boron,gallium,and indium have very rich coordination modes,ten inorganic-organic hybrid borates,coordination polymers constructed by the IIIA elements and organic acids,and coordination polymers constructed by heterometallic and organic acids and borate ligands have been synthesized under ionothermal conditions.These compouds were characterized by elemental analysis,FT-IR spectrum,thermal analysis and X-ray powder diffraction,and their crystal structures were determined by single X-ray crystal diffraction.Of these,four compouds have 3D pore structures.The fluorescence properties,adsorption properties and ion exchange properties of these compouds were also studied.In addition,the adsorption heat of K2Ga(B5O10)·4H2O and Rb2Ga(B5O10)·4H2O in the liquid-solid phase were determined.Details are as follows:Ten novel IIIA compounds,[(CH3)4N][B506(OH)4]·1/2H20,[(CH3)4N][B506(OH)4],Ga(en)2[B5·8(OH)2]H20,In(en)2[B508(OFH)2]·H20,[C6H11N2][Ga(BDC)2],[C7H13N2][Ga(BDC)2],[C6H12N2]2[In2(BDC)3Br2],[C7H13N2]2[In2(BDC)3Br2],[C6H11N2]2[In2Co(OH)2(BTC)2Br2]and Co5[In(BTC)4(B2O4)2(OH)2]were synthesised under ionothermally conditions.[(CH3)4N][B5O6(OH)4]·1/2H2O and[(CH3)4N][B506(OH)4]are isostructural,and both crystallize in the monoclinic system with space group P21/c.The[B5O6(OH)4]-clusters are held together through the O-H…O hydrogen bonds,forming a 3D supramolecular structure.The unit cell dimensions of[(CH3)4N][B5O6(OH)4]·1/2H2O:a = 9.2765(5)A,b =16.8558(10)A,c = 9.2354(6)A,P =96.038(6),Z = 2.The unit cell dimensions of[(CH3)4N][B5O6(OH)4]:a =9.2973(6)A,b-16.9102(11)A,c = 9.2464(12)A,?=96.13(8),Z = 4.Ga(en)2[B5O8(OH)2]·H20 and In(en)2[B5O8(OH)2]H20 are isostructural,and both crystallize in the monoclinic system with space group P21/c.Their structures are characterized as 1D helix chain,and the 1D helical chains are held together through the O-H—O and N-H…O hydrogen bonds,forming a 3D supramolecular structure.The unit cell dimensions of Ga(en)2[B5O8(OH)2]·H2O:a=9.2866(3)A,b=12.3169(3)A,c=14.2910(4)A,?=90°,?= 96.123(3)°,?=90°,V=1625.31(8)A3,Z=4.The unit cell dimensions of In(en)2[B5O8(OH)2]·H20:a=9.3939(2)A,b=12.4805(3)A,c=14.5117(3)A,?=90°,?= 95.088(2)°,?=90°,V=1694.66(6)A3,Z=4.[C6H11N2][Ga(BDC)2]and[C7H13N2][Ga(BDC)2]are isostructural with MOFs structure,and both crystallize in the monoclinic system with space group P21/c.The unit cell dimensions of[C6H11N2][Ga(BDC)2]is a=6.8573(5)A,b=31.1640(19)A,c=11.1749(11)A,?=90°,?= 105.515(8)°,?=90°,V=2301.1(3)A3,Z=4.The unit cell dimensions of[C7H13N2][Ga(BDC)2]is a=6.7957(4)A,b=31.230(2)A,c=1 1.3264(6)A,?=90°,?= 105.087(6)°,?=90°,V=2320.9(2)A3,Z=4.[C6H12N2]2[In2(BDC)3Br2]and[C7H13N2]2[In2(BDC)3Br2]are isostructural,and both crystallize in the monoclinic system with space group P21/c.Their structures are characterized as a novel graphite-like layered structure.The unit cell dimensions of[C6H12N2]2[In2(BDC)3Br2]is a=7.5816(8)A,b=19.2284(18)A,c=14.9297(17)A,?=90°,?=112.072(8)°,?=90°,V=2017.0(4)A3,Z=2.The unit cell dimensions of[C7H13N2]2[In2(BDC)3Br2]is a=7.6468(3)A,b=19.2855(6)A,c=15.2669(6)A,?=90°,?= 112.933(3)°,?=90°,V=2073.49(13)A3,Z=4.[C6H11N2]2[In2Co(OH)2(BTC)2Br2]crystallizes in the monoclinic system with space group P21/c.Its structure is characterized as a 3D open framework..The unit cell dimensions of[C6HI1N2]2[In2Co(OH)2(BTC)2Br2]is a=10.273(7)A,b=11.318(8)A,c=16.461(11)A,?=90°,?=100.064(11)°,?=90°,V=1884(2)A3,Z=2.Co5[In(BTC)4(B204)2(OH)2]crystallizes in the monoclinic system with space group P21/c.Its structure is characterized as a 3D open framework.The unit cell dimensions of Co5[In(BTC)4(B2o4)2(OH)2]is a=11.9109(3)A,b=14.3578(3)A,c=20.6096(6)A,?=90°,?=98.208(2)°,?=90°,V=3488.43(15)A3,Z=2.The fluorescence properties of some synthetic samples were investigated by fluorescence spectrophotometer,especially the effects of different temperatures on the fluorescence properties of[(CH3)4N][B5O6(OH)4]·1/2H2O.The adsorption property of Co5In(BTC)4[(B204(OH)]2,and ion exchange property of[C6H11N2]2[In2Co(OH)2(BTC)2Br2]were also studied.The adsorption heat of K2Ga(B5O10)·4H2O and Rb2Ga(B5O10)·4H2O in organic solvents were measured,and the thermokinetics of the adsorption heat of K2[Ga(B5O10)]·4H2O in methanol were also studied.Performed its thermodynamic properties of experimental analysis to calculate The thermokinetic parameters,such as rate constants,activation energy,pre-exponential factor and reaction order,have been obtained on the basis of thermokinetic model.The results obtained in this paper enrich the type and structure of the IIIA crystal materials,and can provides synthesis method and the physic-chemical data for the application.It also has great significance for the selection of new absorbents. |
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