金属—有机配合物修饰的多金属氧酸盐的合成，结构和表征
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摘要
本论文利用中温水热合成技术,以多金属氧酸盐为基本构筑单元,引入合适的过渡金属离子和有机配体,合成了四种金属-有机配合物修饰的多金属氧酸盐化合物。利用ICP-AES,CHN,IR,单晶X-ray衍射,TG-DSC及CV等手段,研究了他们的组成,结构和性质。探讨了这类化合物的合成条件及过渡金属离子的配位形式和配体的构型等因素对合成化合物结构的影响。
1.以Keggin型结构的磷钨／钼酸盐为基本建筑单元,通过有机配体2,2'-联吡啶-3,3＇-二羧酸(H2bpdc)和铜离子结合,合成了两个新的有机-无机化合物。
{[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2][PW12O40])·9H20 (1)
{[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2][PMo12O40]}·8H20 (2)
化合物(1)和(2)在相似的反应条件下合成,但由于杂多阴离子的不同,而导致其堆积模式的不同。他们都显示出由Cu配合物桥连的杂多阴离子而构成的双链结构。在化合物(1)中,双链彼此通过氢键相连构成层状结构。而化合物(2)中,由于一个铜原子的配位环境不同,双链通过Cu-O键进一步构成二维多孔结构。
2.在水热条件下,K5BW12O4·nH2O,CuSO4·5H2O,2,2'-联吡啶-3,3＇-二羧酸进行原位反应,生成混合价态的超分子化合物
[CuⅠ(2,2'-bipy)2]{[CuⅡ(2,2'-bipy)2]2(BW12O40)}·4H20 (3)
化合物(3)是由双支撑的{[CuⅡ(2,2'-bipy)2]2(BW12O40)}-1的阴离子,通过氢键和π-π堆积作用与水分子和阳离子[CuⅠ(2,2'-bipy)2]+作用,形成超分子化合物。
3.在水热条件下,以(NH4)6Mo7O24·4H2O,CuSO4·5H2O,邻甲苯联胺,乙二胺为原料,合成了一维链状化合物
{(C2H10N2)[Mo3O10]}n(4)
在化合物(4)中,Mo3O10基本结构单元通过桥氧构成一维无机链。质子化的乙二胺位于一维无机链之间,通过氢键与其构成二维层状结构。
Four polyoxometalates modified by metal organic complexes were successfully synthesized under hydrothermal conditions based on the classic type polyoxometalate building blocks, by exploiting appropriate transition metal cations and organic ligands. These complexes have been investigated by ICP-AES, CHN, IR, TG-DSC,CV and X-ray diffractometer analyses. The study on the synthetic conditions and rules for these new compounds and the exploration of relationship between structures and properties of these compounds were carried out.
1. Two new organic-inorganic hybrid compounds have been hydrothermally synthesized by virtue transition metal ion Cu2+and organic ligand 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2bpdc) based on the phosphorus-tunstate/phosphorus-molybdate:
{[Cu4(H2O)5(H2bpdc) (Hbpdc)(bpdc)2][PW12O40]}·9H2O (1)
{[Cu4(H2O)5(H2bpdc) (Hbpdc)(bpdc)2][PMo12O40]}·8H2O (2)
Compounds 1 and 2 were synthesized under identical conditions, except for choosing different polyoxometalate, which induce different packing modes. In compound 1, the adjacent double one-dimensional chains are linked via hydrogen bonding interactions to form a 2D structure. In compound 2, the 2D porous structure is formed via Cu-0 bonding to linking the double chains.
2. A mixed-valence supramolecular compound was synthesized in situ reaction under hydrothermal condition
[CuⅠ(2,2'-bipy)2]{[CuⅡ(2,2'-bipy)2]2(BW12O40)}-4H2O (3)
The supramolecular compound constructed from bisupporting Keggin polyoxoanion cluster, [CuⅠ(2,2'-bipy)2]+coordination polymer fragments and H2O moleculars throughπ-πstacking and hydrogen bonding interactions.
3. Using (NH4) 6Mo7O24·4H2O, CuSO4·5H2O, diphenyl and ethylenediamine as starting material, a 1-D chain-type supramolecular compound have been synthesized{(C2H10N2)[Mo3O10]}n (4)
1.以Keggin型结构的磷钨／钼酸盐为基本建筑单元,通过有机配体2,2'-联吡啶-3,3＇-二羧酸(H2bpdc)和铜离子结合,合成了两个新的有机-无机化合物。
{[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2][PW12O40])·9H20 (1)
{[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2][PMo12O40]}·8H20 (2)
化合物(1)和(2)在相似的反应条件下合成,但由于杂多阴离子的不同,而导致其堆积模式的不同。他们都显示出由Cu配合物桥连的杂多阴离子而构成的双链结构。在化合物(1)中,双链彼此通过氢键相连构成层状结构。而化合物(2)中,由于一个铜原子的配位环境不同,双链通过Cu-O键进一步构成二维多孔结构。
2.在水热条件下,K5BW12O4·nH2O,CuSO4·5H2O,2,2'-联吡啶-3,3＇-二羧酸进行原位反应,生成混合价态的超分子化合物
[CuⅠ(2,2'-bipy)2]{[CuⅡ(2,2'-bipy)2]2(BW12O40)}·4H20 (3)
化合物(3)是由双支撑的{[CuⅡ(2,2'-bipy)2]2(BW12O40)}-1的阴离子,通过氢键和π-π堆积作用与水分子和阳离子[CuⅠ(2,2'-bipy)2]+作用,形成超分子化合物。
3.在水热条件下,以(NH4)6Mo7O24·4H2O,CuSO4·5H2O,邻甲苯联胺,乙二胺为原料,合成了一维链状化合物
{(C2H10N2)[Mo3O10]}n(4)
在化合物(4)中,Mo3O10基本结构单元通过桥氧构成一维无机链。质子化的乙二胺位于一维无机链之间,通过氢键与其构成二维层状结构。
Four polyoxometalates modified by metal organic complexes were successfully synthesized under hydrothermal conditions based on the classic type polyoxometalate building blocks, by exploiting appropriate transition metal cations and organic ligands. These complexes have been investigated by ICP-AES, CHN, IR, TG-DSC,CV and X-ray diffractometer analyses. The study on the synthetic conditions and rules for these new compounds and the exploration of relationship between structures and properties of these compounds were carried out.
1. Two new organic-inorganic hybrid compounds have been hydrothermally synthesized by virtue transition metal ion Cu2+and organic ligand 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2bpdc) based on the phosphorus-tunstate/phosphorus-molybdate:
{[Cu4(H2O)5(H2bpdc) (Hbpdc)(bpdc)2][PW12O40]}·9H2O (1)
{[Cu4(H2O)5(H2bpdc) (Hbpdc)(bpdc)2][PMo12O40]}·8H2O (2)
Compounds 1 and 2 were synthesized under identical conditions, except for choosing different polyoxometalate, which induce different packing modes. In compound 1, the adjacent double one-dimensional chains are linked via hydrogen bonding interactions to form a 2D structure. In compound 2, the 2D porous structure is formed via Cu-0 bonding to linking the double chains.
2. A mixed-valence supramolecular compound was synthesized in situ reaction under hydrothermal condition
[CuⅠ(2,2'-bipy)2]{[CuⅡ(2,2'-bipy)2]2(BW12O40)}-4H2O (3)
The supramolecular compound constructed from bisupporting Keggin polyoxoanion cluster, [CuⅠ(2,2'-bipy)2]+coordination polymer fragments and H2O moleculars throughπ-πstacking and hydrogen bonding interactions.
3. Using (NH4) 6Mo7O24·4H2O, CuSO4·5H2O, diphenyl and ethylenediamine as starting material, a 1-D chain-type supramolecular compound have been synthesized{(C2H10N2)[Mo3O10]}n (4)
引文
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