【作者】 李娜；

【导师】 黄如丹；

【作者基本信息】 北京理工大学 ， 无机化学， 2015， 博士

【摘要】 本论文在水热条件下设计合成了一系列基于含N配体和多金属氧酸盐的无机-有机杂化化合物。通过红外光谱,紫外光谱,热重,元素分析,X-射线粉末衍射和X-射线单晶衍射对一系列化合物的结构进行了表征。探讨了这些化合物在合成过程中,反应物摩尔比、反应时间、反应温度、p H值等条件对其结构产生的影响。对部分化合物的荧光性质,电化学性质,磁性以及催化性质进行了研究。具体包括:1.选用柔性含N有机配体1,3-bis(imidazolyl)propane(bip)和1,4-bis(imidazol)butane(bib),与Keggin型结构的钼磷酸、钨磷酸作用,在过渡金属离子铜,镍和钴存在下,通过调节反应条件,得到了五种基于多金属氧酸盐的无机-有机杂化化合物:[Cu6(bip)12(PMoVI12O40)2(PMoVMoVI11O40O2)]·8H2O(1),[[Cu6(bip)12(PMoV2MoVI10O40)2(PMoV11MoVIO34)]·8H2O(2),[Ni6(bip)12(PMoVI12O40)(PMoVMoVI11O40)2]Cl·6H2O(3),Cu3(bip)6(PMoV3MoVI9O40)(4),[Co5(H2bib)2(Hbib)2(PW9O34)2(H2O)6]·6H2O(5)。在化合物1和3中,过渡金属Cu(1)和Ni(3)分别与bip配体作用,形成3D孔道结构。多金属氧酸盐作为客体分子,包裹在3D孔道中。化合物2,4和5为超分子结构。化合物1-5通过X-射线单晶衍射、元素分析和热重分析等进行了表征。并且进一步测试了化合物的电化学性质和催化烯烃环氧化反应。2.选用刚性三角形含N配体(tib=1,3,5-tris(1-imidazolyl)benzene,和pytpy=4’-(4’’-pyridyl)2,4’:6’,4’’-terpyridine)水热合成了六个新的无机-有机杂化化合物:Na Cu2(tib)4(H2O)4[H2PWVWVI11O40][H2PWVI12O40]·6H2O(6),Cu3(tib)4Cl4[H2PWVI12O40]2·4H2O(7),Co(tib)2[PWV3WVI9O38]·5H2O(8),Cu3(tib)2[P2MoVI5O22(O2)]·4H2O(9),Mn(pytpy)2MoVI4O13(10)和Co(pytpy)2MoVI4O13(11)。X射线单晶衍射表明化合物6-9均为2D层结构。其中在化合物6-8中,存在一条由相邻的两个Keggin型多金属氧酸盐彼此通过端氧W-O-W连接形成的1D无机链,一维链中的多金属氧酸盐的端氧与金属离子进一步配位,形成了2D层结构。化合物10和11中,四钼酸根阴离子通过金属Mn(10)和Co(11)形成2D层结构,层与层之间通过配体桥连,形成3D结构。该类杂化化合物通过X-射线单晶衍射、X-射线粉末衍射、元素分析、红外光谱和热重分析对化合物进行了表征,并且进一步研究了新化合物的电化学性质和催化烯烃环氧化性能。3.选用刚性链状含N配体3-(4-pyridyl)pyrazole(L)合成了六个新的化合物,分别是:[M(HL)2(H2O)2][MoVI6O20][M=Co(12),Ni(13),Cu(14),Zn(15)],[Mn L2(H2O)2][MoVI6O20](16)和(HL)3PMo12O40(17)。X-射线单晶衍射表明化合物12-16是同构的,并且加入的十二钼磷酸盐降解为六钼酸盐,相邻的六钼酸根离子之间通过共用氧形成一维的钼酸盐链,相邻的一维链之间通过过渡金属离子M[M=Co(12),Ni(13),Cu(14),Zn(15),Mn(16)]连接形成2D层结构。化合物17中配体是作为阳离子来平衡整个分子的电荷,并且通过氢键形成3D结构。通过元素分析,X射线粉末衍射(PXRD)和X射线单晶衍射对化合物进行了表征,并且测试了化合物的磁性。4.选择柔性配体bip和bib合成了6个新的基于多金属氧酸盐的无机-有机杂化化合物:(H2bip)2Si W12O40(18),(Hbip)2(H2bip)2(bip)(PMo12O40)2(19),(Hbip1)(H2bip)(PMo12O40)(20),(Hbib)(H2bib)(PMo12O40)·2H2O(21),(H2bib)3(PMo12O40)2(22)和(H4bib2)5(P2MoV4 MoVIO23)2·3H2O(23)。X-射线单晶衍射表明,化合物18-23的结构为杂多金属氧酸盐作为受体分子,与有机电子给体之间通过氢键或静电相互作用形成超分子化合物。采用红外光谱、元素分析、热重分析等手段对其进行了表征,并且研究了化合物18-23的荧光性质和电化学性质。更多还原

【Abstract】 A series of new inorganic-organic compounds based on polyoxometalates have been synthesized by hydrothermal methods, which choose different kinds of N-containing organic ligands in this paper, and the new compounds have novel structures and potential application. These compounds have been characterized by IR, elemental analyses, UV-vis, TG, X-ray single crystal diffractions and PXRD, and partial compounds have also been investigated by electrochemical, magnetic property and catalysis properties. We also studied the connection of synthesis conditions and structures and many factors may influence the structures, for example, ligands, temperature and p H values.1. Five new polyoxometalate(POM)-templated metal-organic frameworks based on flexible ligands, namely, [Cu6(bip)12(PMoVI12O40)2(PMoVMoVI11O40O2)]·8H2O(1), [Cu6(bip)12(PMoV2MoVI10O40)2(PMoV11MoVIO34)]·8H2O(2), [Ni6(bip)12(PMoVI12O40)(PMoVMoVI11O40)2]Cl·6H2O(3), Cu3(bip)6(PMoV3MoVI9O40)(4), [Co5(H2bib)2(Hbib)2(PW9O34)2(H2O)6]·6H2O(5)(bip=1,3-bis(imidazolyl)propane, bib=1,4-bis(imidazolyl)butane) have been obtained under hydrothermal condition and characterized by single-crystal X-ray diffraction analyses, elemental analyses, and thermogravimetric(TG) analyses. Compounds 1 and 3 represent 3D frameworks, and POMs as the guest molecules are incorporated into the the cages which are composed of the ligands and metals, while compounds 2,4 and 5 show 3D frameworks by hydrogen bonds. In addition, the electrochemical property and the catalytic property of compound 1 have also been investigated.2. Six new inorganic–organic hybrids based on rigid triangular N-containing ligands, Na Cu2(tib)4(H2O)4[H2PWVWVI11O40][H2PWVI12O40]·6H2O(6), Cu3(tib)4Cl4[H2PWVI12O40]2·4H2O(7), Co(tib)2[PWV3WVI9O38]·5H2O(8), Cu3(tib)2[P2MoVI5O22(O2)]·4H2O(9), Mn(pytpy)2MoVI4O13(10), and Co(pytpy)2MoVI4O13(11)(tib=1,3,5-tris(1-imidazolyl)benzene),(pytpy=4’-(4’’-pyridyl)2,4’:6’,4’’-terpyridine) have been hydrothermally synthesized. Single crystal X-ray diffraction studies revealed that compounds 6-9 display two-dimensional(2D) layers structure. In compounds 6-8, the adjacent Keggin anions link with each other by W–O–W to form 1D inorganic chains. Compounds 10-11 are 3D “pillar-layer” frameworks based on bimetal-oxide layers pillared by the pytpy ligands. The compounds have been characterized by elemental analysis, powder X-ray diffraction, X-ray photoelectron spectroscopy and thermogravimetric analysis. Moreover, the electrochemical properties and catalytic properties of compound 6 have also been investigated.3. A series of inorganic-organic hybrid materials based on polyoxometalates(POMs), namely, [M(HL)2(H2O)2][MoVI6O20] [M=Co(12), Ni(13), Cu(14), Zn(15)], [Mn L2(H2O)2][MoVI6O20](16), and(HL)3PMo12O40(17) [L=3–(4-pyridyl)pyrazole], have been synthesized. Single-crystal X-ray diffraction indicate that 12-16 are isostructural. It is worth noting that the polyanions are bridged by Mo-O-Mo to form 1D inorganic chains, which are further connected via M ions to form 2D nets. In compound 17, the ligands are used as the positive ions to balance the charge of the compound. The compounds have been characterized by elemental analysis, powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction. Moreover, the magnetic property of compound 16 has also been investigated in detail.4. A series of inorganic=organic hybrid materials based on polyoxometalates(POMs), namely,(H2bip)2Si W12O40(18);(Hbip)2(H2bip)2(bip)(PMo12O40)2(19);(Hbip1)(H2bip)(PMo12O40)(20);(Hbib)(H2bib)(PMo12O40)·2H2O(21);(H2bib)3(PMo12O40)2(22) and(H4bib2)5(P2MoV4 MoVIO23)2·3H2O(23). Single-crystal X-ray diffraction indicate that the ligands are used as the positive ions to balance the charge of the compounds. The compounds have been characterized by IR, elemental analysis, TG, the electrochemical properties and fluorescent property of compound 18 have also been investigated.更多还原