| In this paper,in order to synthesize complexes with diverse structures and different properties,15 complexes were constructed with polymolybdate anions,Keggin-type and Anderson-type polyoxometalates anions,pyridine tetrazole and pyridine amide organic ligands.Their composition and structure were determined by a series of characterization techniques,in-depth exploration of the organic dye degradation functions and electrochemical multifunctional application of some complexes.1.In this chapter,a series of flexible bipyridinetetrazole ligands with different spacer lengths were selected and introduced into the synthesis environment of different polyoxometalates-based complexes under hydrothermal conditions,by which tenpolyoxometalates-based organic-inorganic complexes were obtained.{(4-H2bptzb)2[HPMo12O40]2}·H2O(1){Ag(4-H2bptzb)(H2O)[PMo12O40]}(2){Ag3(3-bptzb)2[PMo12O40]}(3){Ag4(3-bptzpe)3(H2O)2[HPMo12O40]2}(4){Cu2(3-bptzp)3(H2O)4[Si W12O40]}·H2O(5){Cu2(3-bptzpe)2(H2O)8[Si W12O40]}·4H2O(6){Cu2(3-bptzh)3(H2O)6[Si W12O40]}(7){Cu(3-H2bptzh)(H2O)2[?-Mo8O26]}·(3-H2bptzh)·H2O(8){Cu(3-bptzpe)2[?-Mo8O26]}(9){Cu2(3-bptzp)2(H2O)6[?-Mo8O26]}(10){3-bptzb=1,4-bis(5-(3-pyridyl)tetrazolyl)-propane,4-bptzb=1,4-bis(5-(4-pyridyl)tetrazolyl)-propane,3-bptzpe=1,4-bis(5-(3-pyridyl)tetrazolyl)-pentane,3-bptzp=1,4-bis(5-(3-pyridyl)tetrazolyl)-butane,3-bptzh=1,4-bis(5-(3-pyridyl)tetrazolyl)-hexane}In complex 1,there was a free 4-H2bptzb ligand,H3[PMo12O40](PMo12),which then forms a supramolecular structure through weak interaction.Complex 2share the same experimental materials with 1 except that p H value was adjusted to about 1.0.Complex 2 also present a supramolecular structure.On the other side,PMo12anions coordinated with the Ag+ions from the adjacent[Ag2(4-H2bptzb)2]6+loop to afford a discrete dinuclear structure.In complex 3,such 1D chains were connected by two terminal O atoms in PMo12anion and extended into a 2D layer.In complex 4,there were also two crystallographically independent Ag+ions.Each PMo12anions adopted a three-coordinated mode,which connected with two Ag1atoms and two Ag2 atoms to form a[Ag4(PMo12)2]2-metal-inorganic unit.Such loops were connected together by ligands to form a 1D chain.Furthermore,the four-coordinated 3-bptzpe and Ag2 ions linked the neighbouring 1D chains to construct a 2D layer.Complex 5 exhibits a[Si W12O40]4-(Si W12)-based metal-bis(pyridyl-tetrazole)layer.Complex 6 presents a zero-dimensional(0D)structure,the central metal and the ligand formed a metal-organic unit[Cu2(3-bptzpe)2]4+,which incorporate with the Si W12anion by electrostatic interaction.Complex 7 was a one-dimensional metal-organic chain with Si W12anions as uncoordinated templates.Two Cu2+ions were connected by two 3-bptzh ligands to form a loop,which was further joined by the 3-bptzh ligands to form a1D chain.Complex 8 exhibited a 2D?-Mo8O26-based metal-bis(pyridyl-tetrazole)layer.In complex 9,the four-coordinated Cu ion was connected to the?-Mo8O26anion through the Cu-O bond to form a 1D chain,in which the ligand was suspended in a V-shaped conformation.Complex 10 presents a two-dimensional layered structure of metal bis(pyridyl-tetrazole)based on?-Mo8O26.The structural diversities of these complexes show that the p H of the solution and the types of metal ions play a key role in the structure of different complexes.In addition,the carbon nanotube powder(CNT)prepared with complexes 1-4 as the catalyst precursor has a significant adsorption effect on the organic dyes methyl orange.Complexes 5-7 can exhibit high electrocatalytic HER in alkaline and acidic media.In addition,the electrode materials prepared from complexes 8-10 have good capacitance performance under acidic conditions.2.By introducing the pyridine amide ligand into the Anderson-type heteropoly acid system,five functional complexes with polyoxometalates groups were obtained under hydrothermal conditions.H2{Cu2[Al Mo6(OH)6O18]2(3-baph)4(H2O)4}·6H2O(11){Co2(3-Hbaph)2(H2O)4[Cr Mo6(OH)5O19]}·4H2O(12){Co2(3-Hbaph)2(H2O)4[Al Mo6(OH)5O19]}·4H2O(13){Ni2(3-Hbaph)2(H2O)4[Cr Mo6(OH)5O19]}·4H2O(14){Ni2(3-Hbaph)2(H2O)4[Al Mo6(OH)5O19]}·4H2O(15){(3-baph)=N,N?-bis(3-pyridinecarboxamide)-1,2-cyclohexane}Complex 11 was an one-dimensional metal organic chain constructed from Anderson-type[Al Mo6(OH)6O18]3-anions.In addition,complexes 12-15 were isomorphic.Taking the structure of complex 12 as an example,the metal Cu was connected with the terminal oxygen of the polyoxometalates to form a one-dimensional chain,which was further expanded into a two-dimensional layered structure through 3-baph.Finally,the electrochemical behavior of complexes 11-15 and the adsorption performance of organic dyes were studied. |
PDF Full Text Request