有机配体修饰的多金属氧酸盐的合成、表征和性质研究
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摘要
本论文以多金属氧酸盐为基本构筑单元,合成了四种Keggin型多金属氧酸盐化合物。并运用CHN.ICP-AES.IR.UV.TG-DSC及单晶X-射线衍射等测试方法,研究了化合物的组成,结构和性质。探讨了这类化合物的合成条件及影响合成的因素。
1.以Keggin型结构的磷钼酸盐为无机建筑单元,通过有机组分水杨醛缩氨基硫脲的原位反应,合成了一个新的化合物：[(CH3)2NH2]3[PMo12O40](1)
化合物(1)是水杨醛缩氨基硫脲在95%乙醇中经原为反应,转化为二甲胺,并与H3PMo12O40·xH2O作用生成化合物(1)晶体。[PMo12O40]3-单元间通过氢键和静电引力连接构成一维链状结构,质子化的二甲胺在一维链之间通过氢键构成二维层状结构。电化学研究表明,化合物存在两步氧化还原过程。合成化合物对大肠杆菌具有较好的抑菌性能。
2.Keggin型结构的磷钨酸盐、水杨醛缩氨基硫脲在95%乙醇溶液中进行原位反应,得到与化合物(1)相似的一维链状结构的化合物[(CH3)2NH2]3[PW12O40](2)。化合物分子通过氢键形成二维超分子体系。电化学研究表明,化合物存在两步氧化还原过程。合成化合物对大肠杆菌具有较好的抑菌性能。
3.在水热条件下,以Zn/水杨醛缩氨基硫脲配合物为结构单元合成了两种有机配体修饰的多金属氧酸盐：
{[Zn(C8H9N3OS)(C8H10N3OS)][PW12O40]}·3H2O (3)
{[Zn(C8H9N3OS)(C8H10N3OS)][PMo12O40]}·3H2O (4)
并研究了化合物(3)和化合物(4)的电化学性质及抑菌性能。实验结果表明,化合物中杂多阴离子具有Keggin结构类型,每一个[PM12040]3-(M=W, Mo)结构单元通过MO6八面体的端氧或桥氧与[Zn(C8H9N3OS)(C8H10N3OS)]3+单位键合,构成有机配体修饰的多金属氧酸盐。合成化合物对大肠杆菌具有较好的抑菌性能。
Four polyoxometalates complexes were successfully synthesized based on the classic type polyoxometalate building blocks, by exploiting appropriate transition metal cations and organic ligands. These complexes have been investigated by CHN、ICP-AES、IR、UV、TG-DSC and X-ray diffractometer analyses and the study on the composition of the compounds, structure and properties were carried out. And the probe of the synthesis conditions and influence factors of synthesis were carried out.
1. A new polyoxometalates compound have been synthesized based on the phosphomolybdic acid building blocks by in-situ reaction of salicylaldehyde thiosemicarbazone:[(CH3)2NH2]3[PMo12O40] (1)
Compound lwas synthesized by in-situ generation of dimethylamine from salicylaldehyde thiosemicarbazone precursor and effect on H3PMo12O40·xH2O. A one-dimensional chain structure between [PMo12O40]3- units was constituted by hydrogen bonding. Two-dimensional layer structure was constituted by hydrogen bonding base on protonized dimethylamine among the 1D chain. Electrochemical research showed that compound (1) have two steps oxidation and reduction process. Synthetic compounds have good antibacterial properties for e. coli.
2. A one-dimensional chain structure compound [(CH3)2NH2]3[PW12O40] (2) which have similar molecular structure to compound 1 was synthesized by Keggin type phosphotungstic acid and in-situ reaction of salicylaldehyde thiosemicarbazone under the condition of 95% ethanol solution. Compound molecules were constituted by hydrogen bonding, and stable two-dimensional supramolecular system was formed. Electrochemical research showed that compound (2) have two steps oxidation and reduction process. Synthetic compounds have good antibacterial properties for e. coli.
3. Two organic ligand modified polyoxometallates were synthesized by build unit of coordination compound Zn/salicylaldehyde thiosemicarbazone:
{[Zn(C8H9N3OS)(C8H10OS)][PW12O40]}·3H2O (3)
{[Zn(C8H9N3OS)(C8H10OS)][PMo12O40]}·3H2O (4)
Discussed the electrochemical properties and antibacterial properties of compound (3) and compound (4). Experimental results showed that the compounds anions have Keggin type structure. Each [PM12O40]3-(M=W, Mo) structure units and [Zn(C8H9N3OS) (C8H10N3OS)]3+units bonding together through the end oxygen or bridge oxygen of MO6 octahedron, and then constituted organic ligand modified polyoxometallates. Synthetic compounds have good antibacterial properties for e. coli.
1.以Keggin型结构的磷钼酸盐为无机建筑单元,通过有机组分水杨醛缩氨基硫脲的原位反应,合成了一个新的化合物：[(CH3)2NH2]3[PMo12O40](1)
化合物(1)是水杨醛缩氨基硫脲在95%乙醇中经原为反应,转化为二甲胺,并与H3PMo12O40·xH2O作用生成化合物(1)晶体。[PMo12O40]3-单元间通过氢键和静电引力连接构成一维链状结构,质子化的二甲胺在一维链之间通过氢键构成二维层状结构。电化学研究表明,化合物存在两步氧化还原过程。合成化合物对大肠杆菌具有较好的抑菌性能。
2.Keggin型结构的磷钨酸盐、水杨醛缩氨基硫脲在95%乙醇溶液中进行原位反应,得到与化合物(1)相似的一维链状结构的化合物[(CH3)2NH2]3[PW12O40](2)。化合物分子通过氢键形成二维超分子体系。电化学研究表明,化合物存在两步氧化还原过程。合成化合物对大肠杆菌具有较好的抑菌性能。
3.在水热条件下,以Zn/水杨醛缩氨基硫脲配合物为结构单元合成了两种有机配体修饰的多金属氧酸盐：
{[Zn(C8H9N3OS)(C8H10N3OS)][PW12O40]}·3H2O (3)
{[Zn(C8H9N3OS)(C8H10N3OS)][PMo12O40]}·3H2O (4)
并研究了化合物(3)和化合物(4)的电化学性质及抑菌性能。实验结果表明,化合物中杂多阴离子具有Keggin结构类型,每一个[PM12040]3-(M=W, Mo)结构单元通过MO6八面体的端氧或桥氧与[Zn(C8H9N3OS)(C8H10N3OS)]3+单位键合,构成有机配体修饰的多金属氧酸盐。合成化合物对大肠杆菌具有较好的抑菌性能。
Four polyoxometalates complexes were successfully synthesized based on the classic type polyoxometalate building blocks, by exploiting appropriate transition metal cations and organic ligands. These complexes have been investigated by CHN、ICP-AES、IR、UV、TG-DSC and X-ray diffractometer analyses and the study on the composition of the compounds, structure and properties were carried out. And the probe of the synthesis conditions and influence factors of synthesis were carried out.
1. A new polyoxometalates compound have been synthesized based on the phosphomolybdic acid building blocks by in-situ reaction of salicylaldehyde thiosemicarbazone:[(CH3)2NH2]3[PMo12O40] (1)
Compound lwas synthesized by in-situ generation of dimethylamine from salicylaldehyde thiosemicarbazone precursor and effect on H3PMo12O40·xH2O. A one-dimensional chain structure between [PMo12O40]3- units was constituted by hydrogen bonding. Two-dimensional layer structure was constituted by hydrogen bonding base on protonized dimethylamine among the 1D chain. Electrochemical research showed that compound (1) have two steps oxidation and reduction process. Synthetic compounds have good antibacterial properties for e. coli.
2. A one-dimensional chain structure compound [(CH3)2NH2]3[PW12O40] (2) which have similar molecular structure to compound 1 was synthesized by Keggin type phosphotungstic acid and in-situ reaction of salicylaldehyde thiosemicarbazone under the condition of 95% ethanol solution. Compound molecules were constituted by hydrogen bonding, and stable two-dimensional supramolecular system was formed. Electrochemical research showed that compound (2) have two steps oxidation and reduction process. Synthetic compounds have good antibacterial properties for e. coli.
3. Two organic ligand modified polyoxometallates were synthesized by build unit of coordination compound Zn/salicylaldehyde thiosemicarbazone:
{[Zn(C8H9N3OS)(C8H10OS)][PW12O40]}·3H2O (3)
{[Zn(C8H9N3OS)(C8H10OS)][PMo12O40]}·3H2O (4)
Discussed the electrochemical properties and antibacterial properties of compound (3) and compound (4). Experimental results showed that the compounds anions have Keggin type structure. Each [PM12O40]3-(M=W, Mo) structure units and [Zn(C8H9N3OS) (C8H10N3OS)]3+units bonding together through the end oxygen or bridge oxygen of MO6 octahedron, and then constituted organic ligand modified polyoxometallates. Synthetic compounds have good antibacterial properties for e. coli.
引文
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