有机膦酸构筑的多钨氧簇稀土化合物的设计合成、结构及性质
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摘要
在常规水溶液条件下,选择介稳态的前驱体K14[As2W19O67(H2O)]与配体羟基乙叉二膦酸(HEDP)及稀土化合物反应,合成了一例有机膦酸构筑的多钨氧簇稀土化合物Cs H[Pr(H2O)4(AsW9O33)(W2O3)(O3PCOHCH3PO3)Pr(H2O)7]2?19H2O(1),并通过单晶X射线衍射分析、元素分析、傅里叶红外光谱分析等对其结构进行了表征.晶体解析表明,化合物1由1个S形结构框架{[(As W9O33)(W2O3)]2}, 2个有机磷酸基团{O3PCOHCH3PO3}和4个Pr3+离子通过一定的方式键连形成三维框架结构.磁学性质研究表明,化合物1呈现出反铁磁性耦合作用.荧光性质研究表明,化合物1在近红外区呈现出双寿命发光,其中τ1=4.76μs(35.53%),τ2=9.71μs(64.4%).
Polyoxometalates(POMs),a unique class of metal-oxygen clusters with an oxygen-rich surface and high negative charge,have attracted great attention due to their unique structural variety and excellent physicochemical properties.In addition,organophosphonates,as an important kind of organic ligands with wide various and rich coordination modes,have lots of potential applications in materials,medicine and catalysis.Therefore,the synthesis of organophosphonates-based POMs with novel structure and good property is of contemporary interest.Polyoxotungstates(POTs)are viewed as one of the most important and vibrant subfamilies in POM chemistry and have been increasingly used as building blocks for the construction of systems with inorganic-organic hybrid compounds.Nevertheless,compared to the abundant derivatives of polyoxomolybdates and polyoxovanadates,organophosphonate-based POTs have been rarely studied.It is commonly that most of the structures just anchor some common transition metals(Co,Ni,Cu)or even do not anchor any metal ions.In contrast,POTs incorporated with lanthanide(Ln)ions and organophosphonate ligands have been rarely explored.Up to now,only a series of Ln-containing organophosphonatebased POTs have been reported.Moreover,the Ln ions possess the 4f electrons,leading to interesting properties such as magnetic and photoluminescent properties.It appeals us to devote in investigating the interesting Ln-containing organophosphonate-functionalized POTs.Herein,a new organic-inorganic hybrid Cs H[Pr(H_2O)_4(AsW_9O_(33))(W_2O_3)(O_3PCOHCH_3PO_3)Pr(H_2O)_7]_2?19H_2O(1)has been successfully synthesized by reaction of K_(14)[As_2W_(19)O_(67)(H_2O)],HEDP and PrCl_3?6H_2O in a conventional aqueous method.This structure was structurally characterized by single-crystal X-ray diffraction,TG analysis,PXRD and IR spectrum.The results show that compound 1 exhibits a three-dimensional(3D)framework structure which is consist of the S-shaped inorganic building block{[(AsW_9O_(33))(W_2O_3)]_2},four Pr ions and two organophosphonate groups{O_3PCOHCH_3PO_3}.Variable temperature magnetic susceptibility of the solid state 1 was also measured at 1.8-300 K with an applied field of 1 kOe.At 300 K,theχ_mT product is 6.42 cm~3 K mol~(-1),close to the value of 6.40 cm~3 K mol~(-1)expected for four uncoupled Pr~(III) ions(L=5,3H_4,g=4/5,S=1).With cooling,theχ_mT value decreases continuously down to a value of 5.16 cm~3 K mol~(-1) at 101 K.As the temperature further decreases,theχ_mT value starts to decrease rapidly and reaches a minimum of 0.43 cm~3 mol~(-1) K at 1.8 K.This behavior indicates the antiferromagnetic exchange interactions and which is further confirmed by a negative Weiss constantθ=-39.02 K derived by fitting the Curie-Weiss law to the magnetic data between 68 and 300 K The near-infrared(NIR)emission spectra of 1 was also investigated at room temperature.Under the excitation at 448 nm,the NIR emission spectrum of 1 consists of three characteristic peaks of the Pr~(III) ions at 871 nm(~ID_2→~3F_2),1017 nm(~ID_2→~3F_4)and 1515 nm(~1D_2→~1G_4).Moreover,the NIR decay curve of 1 is fitted into a second-order exponential function with lifetimes ofτ_1=4.76μs(35.53%),τ_2=9.71μs(64.47%).In the following work,other bridging ligand with different functional groups such as amino or carboxyl-functionalized organophosphonate will be introduced into this system to explore much more Ln-containing organophosphonate-based POTs with intriguing structures and properties.
Polyoxometalates(POMs),a unique class of metal-oxygen clusters with an oxygen-rich surface and high negative charge,have attracted great attention due to their unique structural variety and excellent physicochemical properties.In addition,organophosphonates,as an important kind of organic ligands with wide various and rich coordination modes,have lots of potential applications in materials,medicine and catalysis.Therefore,the synthesis of organophosphonates-based POMs with novel structure and good property is of contemporary interest.Polyoxotungstates(POTs)are viewed as one of the most important and vibrant subfamilies in POM chemistry and have been increasingly used as building blocks for the construction of systems with inorganic-organic hybrid compounds.Nevertheless,compared to the abundant derivatives of polyoxomolybdates and polyoxovanadates,organophosphonate-based POTs have been rarely studied.It is commonly that most of the structures just anchor some common transition metals(Co,Ni,Cu)or even do not anchor any metal ions.In contrast,POTs incorporated with lanthanide(Ln)ions and organophosphonate ligands have been rarely explored.Up to now,only a series of Ln-containing organophosphonatebased POTs have been reported.Moreover,the Ln ions possess the 4f electrons,leading to interesting properties such as magnetic and photoluminescent properties.It appeals us to devote in investigating the interesting Ln-containing organophosphonate-functionalized POTs.Herein,a new organic-inorganic hybrid Cs H[Pr(H_2O)_4(AsW_9O_(33))(W_2O_3)(O_3PCOHCH_3PO_3)Pr(H_2O)_7]_2?19H_2O(1)has been successfully synthesized by reaction of K_(14)[As_2W_(19)O_(67)(H_2O)],HEDP and PrCl_3?6H_2O in a conventional aqueous method.This structure was structurally characterized by single-crystal X-ray diffraction,TG analysis,PXRD and IR spectrum.The results show that compound 1 exhibits a three-dimensional(3D)framework structure which is consist of the S-shaped inorganic building block{[(AsW_9O_(33))(W_2O_3)]_2},four Pr ions and two organophosphonate groups{O_3PCOHCH_3PO_3}.Variable temperature magnetic susceptibility of the solid state 1 was also measured at 1.8-300 K with an applied field of 1 kOe.At 300 K,theχ_mT product is 6.42 cm~3 K mol~(-1),close to the value of 6.40 cm~3 K mol~(-1)expected for four uncoupled Pr~(III) ions(L=5,3H_4,g=4/5,S=1).With cooling,theχ_mT value decreases continuously down to a value of 5.16 cm~3 K mol~(-1) at 101 K.As the temperature further decreases,theχ_mT value starts to decrease rapidly and reaches a minimum of 0.43 cm~3 mol~(-1) K at 1.8 K.This behavior indicates the antiferromagnetic exchange interactions and which is further confirmed by a negative Weiss constantθ=-39.02 K derived by fitting the Curie-Weiss law to the magnetic data between 68 and 300 K The near-infrared(NIR)emission spectra of 1 was also investigated at room temperature.Under the excitation at 448 nm,the NIR emission spectrum of 1 consists of three characteristic peaks of the Pr~(III) ions at 871 nm(~ID_2→~3F_2),1017 nm(~ID_2→~3F_4)and 1515 nm(~1D_2→~1G_4).Moreover,the NIR decay curve of 1 is fitted into a second-order exponential function with lifetimes ofτ_1=4.76μs(35.53%),τ_2=9.71μs(64.47%).In the following work,other bridging ligand with different functional groups such as amino or carboxyl-functionalized organophosphonate will be introduced into this system to explore much more Ln-containing organophosphonate-based POTs with intriguing structures and properties.
引文
1 Katsoulis D E.A survey of applications of polyoxometalates.Chem Rev,1998,98:359-388
2 Marrot J,Pilette M A,Haouas M,et al.Polyoxometalates paneling through{Mo2O2S2}coordination:Cation-directed conformations and chemistry of a supramolecular hexameric scaffold.J Am Chem Soc,2012,134:1724-1737
3 Hill C L.Progress and challenges in polyoxometalate-based catalysis and catalytic materials chemistry.J Mol Catal A Chem,2007,262:2-6
4 Li Z,Li X X,Yang T,et al.Four-shell polyoxometalates featuring high-nuclearity ln26 clusters:Structural transformations of nanoclusters into frameworks triggered by transition-metal ions.Angew Chem Int Ed,2017,56:2664-2669
5 Jin L,Zhu Z K,Wu Y L,et al.Record high-nuclearity polyoxoniobates:Discrete nanoclusters{Nb114},{Nb81},and{Nb52},and extended frameworks based on{Cu3Nb78}and{Cu4Nb78}.Angew Chem Int Ed,2017,56:16288-16292
6 Kortz U,Jameson G B,Pope M T.Polyoxometalate diphosphate complexes.Folded macrocyclic dodecatungstates,[(O3PXPO3)4W12O36]16-(X=O,CH2).J Am Chem Soc,1994,116:2659-2660
7 Mayer C R,Thouvenot R.Organophosphoryl derivatives of trivacant tungstophosphates of general formulaγ-A-[PW9O34(RPO)2]5-:Synthesis and structure determination by multinuclear magnetic resonance spectroscopy(31P,183W).J Chem Soc Dalton Trans,1998,(1):7-14
8 Mayer C R,Herson P,Thouvenot R.Organic-inorganic hybrids based on polyoxometalates.5.1Synthesis and structural characterization of bis(organophosphoryl)decatungstosilicates[γ-SiW10O36((RPO)2]4-.Inorg Chem,1999,38:6152-6158
9 Mayer C R,Hervé,Lavanant H,et al.Hybrid cyclic dimers of divacant heteropolyanions:Synthesis,mass spectrometry(MALDI-TOFand ESI-MS)and NMR multinuclear characterisation.Eur J Inorg Chem,2004,2004:973-977
10 Driss H,Boubekeur K,Debbabi M,et al.Synthesis and spectroscopic characterization of organophosphono derivatives of lindqvist niobotungstates-X-ray crystal structures of(n Bu4N)3[NbW10O38(RP)2](R=n Bu,Hep and Ph).Eur J Inorg Chem,2008,2008:3678-3686
11 Carraro M,Modugno G,Sartorel A,et al.Optically active polyoxotungstates bearing chiral organophosphonate substituents.Eur J Inorg Chem,2009,2009:5164-5174
12 El Moll H,Dolbecq A,Marrot J,et al.A stable hybrid bisphosphonate polyoxometalate single-molecule magnet.Chem Eur J,2012,18:3845-3849
13 El Moll H,Rousseau G,Dolbecq A,et al.Properties of a tunable multinuclear nickel polyoxotungstate platform.Chem Eur J,2013,19:6753-6765
14 Bentaleb F,Makrygenni O,Brouri D,et al.Efficiency of polyoxometalate-based mesoporous hybrids as covalently anchored catalysts.Inorg Chem,2015,54:7607-7616
15 Huo Y,Huo Z,Ma P,et al.Polyoxotungstate incorporating organotriphosphonate ligands:Synthesis,characterization,and catalytic for alkene epoxidation.Inorg Chem,2014,54:406-408
16 Huo Y,Li D,Wan R,et al.Synthesis and characterization of organotriphosphonate-functionalized TM-containing polyoxotungstates.RSC Adv,2015,5:106077-106082
17 Ban R,Sun X,Wang J,et al.Polyoxotungstate incorporating organotriphosphonate ligands and lanthanide ions:Syntheses,characterization,magnetism and photoluminescence properties.Dalton Trans,2017,46:5856-5863
18 Kortz U,Savelieff M G,Bassil B S,et al.A large,novel polyoxotungstate:[As6W65O217(H2O)7]26-.Angew Chem Int Ed,2001,40:3384-3386
19 Pradeep C P,Long D L,Cronin L.Cations in control:Crystal engineering polyoxometalate clusters using cation directed self-assembly.Dalton Trans,2010,39:9443-9457
20 Knoth W H,Harlow R L.New tungstophosphates:Cs6W5P2O23,Cs7W10PO36,and Cs7Na2W10PO37.J Am Chem Soc,1981,103:1865-1867
21 Canny J,Teze A,Thouvenot R,et al.Disubstituted tungstosilicates.1.Synthesis,stability,and structure of the lacunary precursor polyanionγ-SiW10O368-.Inorg Chem,1986,25:2114-2119
22 Brown I D,Altermatt D.Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database.Acta Crystallogr Sect B Struct Sci,1985,41:244-247
23 Ritchie C,Speldrich M,Gable R W,et al.Utilizing the adaptive polyoxometalate[As2W19O67(H2O)]14-to support a polynuclear lanthanoid-based single-molecule magnet.Inorg Chem,2011,50:7004-7014
24 Ban R,Liang Y,Ma P,et al.Synthesis,crystal structure,characterization and magnetic property of a new organophosphonate-based polyoxovanadate.Inorg Chem Commun,2016,71:65-67
25 Dang S,Yu J,Wang X,et al.NIR-luminescence from ternary lanthanide[HoIII,PrIII and TmIII]complexes with 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate.J Lumin,2011,131:1857-1863
2 Marrot J,Pilette M A,Haouas M,et al.Polyoxometalates paneling through{Mo2O2S2}coordination:Cation-directed conformations and chemistry of a supramolecular hexameric scaffold.J Am Chem Soc,2012,134:1724-1737
3 Hill C L.Progress and challenges in polyoxometalate-based catalysis and catalytic materials chemistry.J Mol Catal A Chem,2007,262:2-6
4 Li Z,Li X X,Yang T,et al.Four-shell polyoxometalates featuring high-nuclearity ln26 clusters:Structural transformations of nanoclusters into frameworks triggered by transition-metal ions.Angew Chem Int Ed,2017,56:2664-2669
5 Jin L,Zhu Z K,Wu Y L,et al.Record high-nuclearity polyoxoniobates:Discrete nanoclusters{Nb114},{Nb81},and{Nb52},and extended frameworks based on{Cu3Nb78}and{Cu4Nb78}.Angew Chem Int Ed,2017,56:16288-16292
6 Kortz U,Jameson G B,Pope M T.Polyoxometalate diphosphate complexes.Folded macrocyclic dodecatungstates,[(O3PXPO3)4W12O36]16-(X=O,CH2).J Am Chem Soc,1994,116:2659-2660
7 Mayer C R,Thouvenot R.Organophosphoryl derivatives of trivacant tungstophosphates of general formulaγ-A-[PW9O34(RPO)2]5-:Synthesis and structure determination by multinuclear magnetic resonance spectroscopy(31P,183W).J Chem Soc Dalton Trans,1998,(1):7-14
8 Mayer C R,Herson P,Thouvenot R.Organic-inorganic hybrids based on polyoxometalates.5.1Synthesis and structural characterization of bis(organophosphoryl)decatungstosilicates[γ-SiW10O36((RPO)2]4-.Inorg Chem,1999,38:6152-6158
9 Mayer C R,Hervé,Lavanant H,et al.Hybrid cyclic dimers of divacant heteropolyanions:Synthesis,mass spectrometry(MALDI-TOFand ESI-MS)and NMR multinuclear characterisation.Eur J Inorg Chem,2004,2004:973-977
10 Driss H,Boubekeur K,Debbabi M,et al.Synthesis and spectroscopic characterization of organophosphono derivatives of lindqvist niobotungstates-X-ray crystal structures of(n Bu4N)3[NbW10O38(RP)2](R=n Bu,Hep and Ph).Eur J Inorg Chem,2008,2008:3678-3686
11 Carraro M,Modugno G,Sartorel A,et al.Optically active polyoxotungstates bearing chiral organophosphonate substituents.Eur J Inorg Chem,2009,2009:5164-5174
12 El Moll H,Dolbecq A,Marrot J,et al.A stable hybrid bisphosphonate polyoxometalate single-molecule magnet.Chem Eur J,2012,18:3845-3849
13 El Moll H,Rousseau G,Dolbecq A,et al.Properties of a tunable multinuclear nickel polyoxotungstate platform.Chem Eur J,2013,19:6753-6765
14 Bentaleb F,Makrygenni O,Brouri D,et al.Efficiency of polyoxometalate-based mesoporous hybrids as covalently anchored catalysts.Inorg Chem,2015,54:7607-7616
15 Huo Y,Huo Z,Ma P,et al.Polyoxotungstate incorporating organotriphosphonate ligands:Synthesis,characterization,and catalytic for alkene epoxidation.Inorg Chem,2014,54:406-408
16 Huo Y,Li D,Wan R,et al.Synthesis and characterization of organotriphosphonate-functionalized TM-containing polyoxotungstates.RSC Adv,2015,5:106077-106082
17 Ban R,Sun X,Wang J,et al.Polyoxotungstate incorporating organotriphosphonate ligands and lanthanide ions:Syntheses,characterization,magnetism and photoluminescence properties.Dalton Trans,2017,46:5856-5863
18 Kortz U,Savelieff M G,Bassil B S,et al.A large,novel polyoxotungstate:[As6W65O217(H2O)7]26-.Angew Chem Int Ed,2001,40:3384-3386
19 Pradeep C P,Long D L,Cronin L.Cations in control:Crystal engineering polyoxometalate clusters using cation directed self-assembly.Dalton Trans,2010,39:9443-9457
20 Knoth W H,Harlow R L.New tungstophosphates:Cs6W5P2O23,Cs7W10PO36,and Cs7Na2W10PO37.J Am Chem Soc,1981,103:1865-1867
21 Canny J,Teze A,Thouvenot R,et al.Disubstituted tungstosilicates.1.Synthesis,stability,and structure of the lacunary precursor polyanionγ-SiW10O368-.Inorg Chem,1986,25:2114-2119
22 Brown I D,Altermatt D.Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database.Acta Crystallogr Sect B Struct Sci,1985,41:244-247
23 Ritchie C,Speldrich M,Gable R W,et al.Utilizing the adaptive polyoxometalate[As2W19O67(H2O)]14-to support a polynuclear lanthanoid-based single-molecule magnet.Inorg Chem,2011,50:7004-7014
24 Ban R,Liang Y,Ma P,et al.Synthesis,crystal structure,characterization and magnetic property of a new organophosphonate-based polyoxovanadate.Inorg Chem Commun,2016,71:65-67
25 Dang S,Yu J,Wang X,et al.NIR-luminescence from ternary lanthanide[HoIII,PrIII and TmIII]complexes with 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate.J Lumin,2011,131:1857-1863