氨基酚系列取代的六钼氧酸盐的合成、表征及进一步官能团化
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摘要
多金属氧酸盐(polyoxometalates,简写为POMs),通常称为多酸(盐),是由前过渡金属离子通过氧连接而形成的金属-氧簇类化合物。由于多酸具有储存电子、质子的性能,是一类优秀的受体分子,可以与无机分子、有机分子(包括大环化合物)、离子等结合形成超分子化合物。多金属氧簇的有机亚胺衍生物,由于多会属氧簇的金属d-轨道与芳香亚胺共轭体系的π轨道互相作用而产生新的电子结构和相应的理化性能。通过分子设计合成各种多金属氧簇有机亚胺衍生物,研究这些新化合物的结构,性能及其之间的关系,探索和开发新的催化剂、导电材料和光电材料等。
本人在前人研究的基础上,采用DCC脱水法详细研究适合于多酸衍生物的合成化学,采用氨基酚系列化合物为配体,对Lindqvist结构类型的含钼多酸根及其衍生物进行化学修饰,并进而利用酯化反应对其作进一步的化学修饰,从而实现钼酸根有机亚胺衍生物分子的功能团化。因此,通过本论文的研究,可以拓展多酸衍生物的制备途径,了解和发现该类有机-无机杂化材料新奇的结构和特异的性能,并为该类化合物在实际工作中的应用提供一定的指导。
本人合成了三种新的六钼酸盐有机亚胺衍生物,并测定了对氨基酚双取代衍生物的晶体结构,还通过酯化反应对邻氨基酚单取代衍生物作进一步官能团化。同时发现六钼酸盐的同质多晶现象并测定了其结构。对新合成的六钼酸盐有机亚胺衍生物进行了元素分析、IR、及UV-Vis研究,并选择性地对部分化合物进行了~1H NMR和X-射线单晶结构解析的表征,并探讨了这类化合物的DCC脱水法反应条件,寻求最佳反应条件。
The previous transition metal ions combining with oxide are able to form molecular metal-oxide cluster anions,commonly referred to as polyoxometalates or polyoxoanions(POMs).They are good receptor molecules because of the properties of POMs such as the storage of clectrou and proton,the supramolecular compounds can be combined with inorganic elements,organic molecules(including macrocyclic compounds)and ion.More excellent properties of these organoimido derivatives can be adjusted by strong d-πinteractions between POM and organic imide ligand.where space occupied by conjugationπelectron of the ligand may be extended to the inorganic framework of POM.The aim of is to prepare new organoimido derivatives of POMs in the light of the principles of molecule design.The researches on structures,properties and structure-property relationships of the novel compounds will play an important part in explorations and developments of new catalyzers,electric-materials and photoelectric-materials.
In this dissertation,on the basis of previous studies,using DCC dehydration method suitable for more study of the synthesis of acid derivatives,compounds used for paracetamol series ligand,Lindqvist type structure containing molybdenum more radical and chemically modified derivatives,and its use of esterification for further chemical modification. thus achieving molybdenum imine derivatives organic radical elements of the functional groups.Therefore,the dissertation research,can expand acid derivatives preparation,understanding the structure and specific pcrformance of such organic-inorganic hybrid materials,this makes it important for the guidance of the compounds in the actual work.
In this dissertation,three new organoimido derivatives has been synthesized by DCC dehydration method.and(n-Bu_4N)_2[Mo_6O_(18)≡(NAr)_2] (Ar=p-C_6H_4OH)has been structurally characterized by X-ray single crystal diffraction.Through the esterification of(n-Bu_4N)_2[Mo_6O_(18)≡NAr] (Ar=o-C_6H_4OH)for further function.Polymorphism has been discovered in organoimido and characterized their structure.All the new complexes were characterized by Elemental analysis,IR,and UV-Vis.Some of the complexes were also characterized by ~1H NMR and thermogravi- metric analysis.The researches on synthesis reactions for these hybrid compounds have been done,in order to look for the optimal conditions.
本人在前人研究的基础上,采用DCC脱水法详细研究适合于多酸衍生物的合成化学,采用氨基酚系列化合物为配体,对Lindqvist结构类型的含钼多酸根及其衍生物进行化学修饰,并进而利用酯化反应对其作进一步的化学修饰,从而实现钼酸根有机亚胺衍生物分子的功能团化。因此,通过本论文的研究,可以拓展多酸衍生物的制备途径,了解和发现该类有机-无机杂化材料新奇的结构和特异的性能,并为该类化合物在实际工作中的应用提供一定的指导。
本人合成了三种新的六钼酸盐有机亚胺衍生物,并测定了对氨基酚双取代衍生物的晶体结构,还通过酯化反应对邻氨基酚单取代衍生物作进一步官能团化。同时发现六钼酸盐的同质多晶现象并测定了其结构。对新合成的六钼酸盐有机亚胺衍生物进行了元素分析、IR、及UV-Vis研究,并选择性地对部分化合物进行了~1H NMR和X-射线单晶结构解析的表征,并探讨了这类化合物的DCC脱水法反应条件,寻求最佳反应条件。
The previous transition metal ions combining with oxide are able to form molecular metal-oxide cluster anions,commonly referred to as polyoxometalates or polyoxoanions(POMs).They are good receptor molecules because of the properties of POMs such as the storage of clectrou and proton,the supramolecular compounds can be combined with inorganic elements,organic molecules(including macrocyclic compounds)and ion.More excellent properties of these organoimido derivatives can be adjusted by strong d-πinteractions between POM and organic imide ligand.where space occupied by conjugationπelectron of the ligand may be extended to the inorganic framework of POM.The aim of is to prepare new organoimido derivatives of POMs in the light of the principles of molecule design.The researches on structures,properties and structure-property relationships of the novel compounds will play an important part in explorations and developments of new catalyzers,electric-materials and photoelectric-materials.
In this dissertation,on the basis of previous studies,using DCC dehydration method suitable for more study of the synthesis of acid derivatives,compounds used for paracetamol series ligand,Lindqvist type structure containing molybdenum more radical and chemically modified derivatives,and its use of esterification for further chemical modification. thus achieving molybdenum imine derivatives organic radical elements of the functional groups.Therefore,the dissertation research,can expand acid derivatives preparation,understanding the structure and specific pcrformance of such organic-inorganic hybrid materials,this makes it important for the guidance of the compounds in the actual work.
In this dissertation,three new organoimido derivatives has been synthesized by DCC dehydration method.and(n-Bu_4N)_2[Mo_6O_(18)≡(NAr)_2] (Ar=p-C_6H_4OH)has been structurally characterized by X-ray single crystal diffraction.Through the esterification of(n-Bu_4N)_2[Mo_6O_(18)≡NAr] (Ar=o-C_6H_4OH)for further function.Polymorphism has been discovered in organoimido and characterized their structure.All the new complexes were characterized by Elemental analysis,IR,and UV-Vis.Some of the complexes were also characterized by ~1H NMR and thermogravi- metric analysis.The researches on synthesis reactions for these hybrid compounds have been done,in order to look for the optimal conditions.
引文
[1]王恩波,胡长文.许林.多酸化学导论[M].北京:化学工业出版社,1998.
[2]Pope M T,王恩波等译.杂多和同多金属氧酸盐[M].长春:吉林大学出版社,1991.
[3]中国科学院2001科学发展报告.[M].北京:科学出版社,2001.
[4]王秀丽,赵岷.多酸电化学导论.[M].北京:中国环境科学出版社.2006.
[5]Hu C.W.,He Q.L.,Zhang Y.H.,Liu Y.Y.,Zhang Y.F.,Tang T.D.,Zhang J.Y..Wang E.B.,Synthesis of new types of polyoxometallate pillared anionic clays:31P and 27Al MAS NMR study of the orientation of intercalated PW_(11)VO_(40)~(-)[J].Chem.Soc.,Chem.Com mun..1996:121-122.
[6]彭军,刘杰,王恩波.Crystal structure or mixed sodium.potassium paradodecatungstate 6-hydr[J].结构化学,1999,18(4):239-244.
[7]许林,王恩波,胡长文,多金届氧酸盐作为构筑块自装合成新型功能分子材料[J].无机化学学报.2000.16(2):218-228
[8]刘杰,王恩波.钻取代型钼硅杂多蓝稀土盐的合成及性质研究[J].高等学校化学学报.1998.19(8):1200-1204
[9]Coronade E.,Gomez-Garcia C.J.,Polyoxometalate-based molecular materials[J].Chem.Rev.,1998.98:273-295.
[10]Rosenheim A,Bilecki R.Iso- and hetero-poly Acids.Ⅷ.Molybdic Acid Alkylarsinates[J].Berlin.Chem.Ber..1913,46:5.39-557.
[11]Du,Y.,Rheingold,A.L.,Maatta,E.A.A polyoxometalate incorporating an organoimido ligand:preparation and structure of[Mo_5O_(18)(MoNC_6H_4CH_3)~(2-)[J].Am.Chem.Soc.1992.114(11:345-346.
[12]Proust A.,Thouvenot R.,Chaussade M.,Robert F.,Gouzerh P.Phenylimido derivatives of[Mo_6O_(19)]~(2-)(?)syntheses.X-ray structures,cibrational,electrochemical.~(95)Mo and ~(14)N NMR studies[J].Inorg.Chim.Acta.1994,224(1-2):81-95.
[13]Clegg W.,R.Errington J.,Fraser K.A..Lax C..Richards D.G.In:Polyoxometalatcs:From Platonic Solids to Anti-Retroviral Activity,M.T.Pope.A.Muller(Eds.).Khlwer.Dordrecht.1994.352:113-115.
[14]Mohs T.R.Yap G.P.A..Rhcingold A.L..Maatta E.A..An Organoimido Derivative of the Hexatungstate Cluster:preparation and structure of[W_6O_(18)(NAr)]~(2-).(Ar=2.6-(i-Pr)_2C_6H_3)[J].lnorg.Chem.1995,34(1):9-10.
[15]Wu P.F.,Li Q.,Ge N.,Wei Y.G.,Wang Y.,Wang P.,Guo H.Y..An Easy Route to Monofunctionalized Organoimido Derivatives of the Lindqvist Hexamolybdate[J].Eur.J.Inorg.Chem.2004,268(14):2819-2822.
[16]Li Q.,Wu P.F..Wei Y.G.,Xia Y.,Wang Y.,Guo H.Y.,Orangic-inorganic hybrids:prcparation and structural characterization of(Bu_4N)_2[Mo_6O_(17)(NAr)_2]and(Bu_4N)_2[Mo_6O_(18)(NAr)](Ar=o-CH_3C_6H_4)[J].Z.Anorg.Allg.Chcm..2005.631:773-779.
[17]Xu.L,Lu.M,Xu.B.B..Wei Y.G.Peng Z.H.,Powell.D.R,Towards main-chain-polyoxometalate containing hybrid polymers:A highly efficient approach to bifunctionalized organoimido derivatives of hexamolybdates[J].Angew.Chem.Int.Ed.Engl.2002,41(21):4129-4132.
[18]Wei Y.G.,Lu.M..Cheung.C.F.C.,Barncs.C.L..Peng Z.H..Functionalization of[MoW_5O_(19)]~(2-)with aromatic aminesisynthesis of the first arylimido derivatives of mixed-metal polyoxometalates[J].lnorg.Chem,2001.40122):5489-5490.
[19]Wet Y.G.,Xu B.L..Barnes,Charles L.,Peng Z.H.,An efficient and convenient reaction protocol to organomido derivarises of polyoxometalates[J].Am.Chem.Soc,2001.123(27):4083-4084.
[20]Gouzerh.P.Proust.A.Main-Group Element.Organic,and Organomctallic Derivatives of Polyoxometalates[J].Chem.Rev.,1998,98:77-111.
[21]Xu.Bubin,Wei.Yongge,Barnes,Charles L.,Peng.Zhonghua.Hybrid molecular materials based on covalently linked inorganic polyoxometalates and organic conjugated systems[J].Angew.Chem.,Int.Ed.Engl..2001.40(12):2290-2292.
[22]Knoth W.H..Derivatives of heteropolyanions(?)Organic derivatives of W_(12)SiO_(40)~(4-).W_(12)PO_(40)~(3-).and Mo_(12)SiO_(40)~(4-)[J].Am.Chem.Soc.,1979,101(3):759-760.
[23]Xu B.B.,Wei Y.G.,Barnes C.L.,et al.Angew Chem.2001.113:2353-2354.
[24]魏永革.多酸类化合物的化学修饰-多钼-氧簇的氮配体官能团化,国家自然科学基金申请书,批准号:20201001.2002
[25]Raynaud M,Chermann J C,Plata F et al.C.R.Polyoxometalates in Medicine[J].Acad.Sci..Ser D.1971,272:347.
[26]胡长文.梁虹,王恩波.杂多峻的催化技术进展[J].现代化工.1992,(4):36
[27]王恩波.杂多酸催化剂连续法合成乙峻乙酯[J].催化学报.1993.14(2):147.
[28]吴通好.李建庆.杨洪茂,王国甲.两种结构钼磷酸的催化氧化行为[J].高等学校化学学报.1991.12(10):1378-1381.
[29]Yamase T.Fujita H.Fukushima K.Medical chemistry of polyoxometalales.Part Ⅰ.Potent antitumor activity of polyoxomolybdates on animal transplantable tumors[J].Inorg.Chem Acta.1988.151:15-18.
[30]Strong.JB..Yap.G.P.A.,Ostrander.R,Liable-sands.L.M..Rheingold.A.,Maatta.E.A.A New Class of Functionalized Polyoxometalates:Synthetic,Structural,Spectroscopic and Electrochemical Studies of Organoimido Derivatives of [Mo_6O_(19)]~(2-)[J].Am.Chem.Soc.2000.122(4):639-649.
[31]Proust A,Gouzerh P,Robert F.Molybdenum oxo nitrosyl complexes(?)Defeet Lindqvist compounds of the type [Mo_5O_(13)(OR)_4(NO)]~(3-)(R=CH_3,C_2H_5).Solid-state interactions with alkali-metal cations[J].Inorg.Chem.,1993.32(23):5291-5298.
[32]Chen Q,Salt J,Zubieta J,Synthesis and structural characterization of binuclear vanadium-oxo- organophosphonato complexes:building blocks for oxovanadium organophosphonate solids[J],Inorg.Chem.,1993.32(21):4485-4486.
[33]Tolkacheva E O.Popov K I.Dyatlova N.Phosphorus-~(31)NMR study of the complex formation in aqueous solutions of l-hydroxyethylenediphosphonic acid(H_5L)with molybdenum[Ⅵ)[J].Russ.Inorg.Chem..1992.37(7):1618-1625.
[34]Khan M I.Chen Q.Zubieta J.Oxomolybdenum(Ⅴ)potyanion clusters.Hydrothermal syntheses and structures of {(NH_4)_5Na_4{Na[Mo_6O_(12)(OH)_3(O_3PC_6H_5]_4}_2}·6H_2O(C_6H_5CH_2NMe_3)_4K_4{K_2[Mo_6O_(12)(OH)_3-(O_3PC_6H_5)_4]_2}·10H_2O and their relationship to the binuclear(Et_4N)[Mo_2O_4C_(13)(H_2O)_3]·5H_2[J].Inorg.Chem.Acta..1995,235(1-2):135-145.
[35]Ban S,Liu S.Shaikh S et aI.Molybdenum-95 NMR studies of taryldiazenido)- and torganohydra(?)do)molybd(?)es.Crystal and molecular structure of[n-Bu_4N]_3[Mo_6O_(18)(NC_6F_5][J].Inorg.Chem.,1988.27(20):3535-3543.
[36]J.T.,Rhule C.L.Hill,A.J.Deborah.Polyoxometalates in Medicine[J].Chem.Rev.1998.98(1):327-358.
[37]Lu M,Wei Y.G,Xu B,Cheung C.F.-C.,Peng Z.H,Powell D.Hybrid Molecular Dumbbells:Bridging Polyoxometalate Clusters with an Organic-Conjugated Rod[J].Angew.Chem.2002.41:1566-1568.
[38]Xu L,Lu M.Xu B.Wei Y.G,Peng,Z:Powell.D.R.Towards Main-Chain-Polyoxometatate-Containing(?)ybrid Polymers(?) Highly Efficient Approach to Bifunctionalizcd Organoimido Derivatives of Hexamolybdates[J]Angew Chem Int Ed.Engl,2003,41:4129-4132.
[39]Xu,B.B.Lu,M,Kang,J et al.Synthcsis and Optical Properties of Conjugated Polwners Containing Polyoxometalate Clusters as Side-Chain Pendants[J].Chcm.Mater.2005.17:2841-2851.
[40]Xu,B.B,Wei.Y.G.Barnes.C.L et al.Polyoxometalate composite Langmuir-Blodgett films:Preparation.struetural characterization and potential optoelectronic applications[J].Angew.Chem.2001,113:2353。
[41]Peng Z.H.Rational synthesis ofcovalently bonded organic-inorganic hydrids[J].Angew.Chem.Int.Ed.2004.43:930-935.
[42]Moore A.R,Kwen H.Beatty A.M,Maatta E.A.Organoimido-polyoxometalates as polymer pendants[J].Chem.Commun.2000:1793-1794.
[43]史亚鹏.有机基团取代的多钼氧酸盐的合成、结构及性质研究[D].西安:西北大学.2006.
[44]夏芸.新型多金属氧簇有机-无机分子基杂化化合物-六钼酸盐的有机亚胺衍生物的研究[D].北京:北京化工大学.2005.
[45]李强.魏永革,王远.郭洪猷.多酸有机亚胺衍生物的紫外-可见光谱及其取代基效应[J].光谱学与光谱分析,2005,25(6):923-926.
[46]田丹碧.仪器分析[M].北京:化学工业出版版社.2004
[47]夏芸,魏永革,郭洪猷.单取代多金属氧酸盐有机亚胺衍生物(n-Bu_4N)_2[Mo_6O_(18)(≡NAr)](Ar=o-CH_3OC_6H_4)的合成[J].化学学报,2005,63(20):1931-1935.
[48]荣国斌.波谱数据表-有机化合物的结构解析[M].上海:华东理工大学出版社.2000.
[49]李强.多酸有机亚胺衍生物的合成、结构与性能研究[D].北京:北京化工大学.2005.
[2]Pope M T,王恩波等译.杂多和同多金属氧酸盐[M].长春:吉林大学出版社,1991.
[3]中国科学院2001科学发展报告.[M].北京:科学出版社,2001.
[4]王秀丽,赵岷.多酸电化学导论.[M].北京:中国环境科学出版社.2006.
[5]Hu C.W.,He Q.L.,Zhang Y.H.,Liu Y.Y.,Zhang Y.F.,Tang T.D.,Zhang J.Y..Wang E.B.,Synthesis of new types of polyoxometallate pillared anionic clays:31P and 27Al MAS NMR study of the orientation of intercalated PW_(11)VO_(40)~(-)[J].Chem.Soc.,Chem.Com mun..1996:121-122.
[6]彭军,刘杰,王恩波.Crystal structure or mixed sodium.potassium paradodecatungstate 6-hydr[J].结构化学,1999,18(4):239-244.
[7]许林,王恩波,胡长文,多金届氧酸盐作为构筑块自装合成新型功能分子材料[J].无机化学学报.2000.16(2):218-228
[8]刘杰,王恩波.钻取代型钼硅杂多蓝稀土盐的合成及性质研究[J].高等学校化学学报.1998.19(8):1200-1204
[9]Coronade E.,Gomez-Garcia C.J.,Polyoxometalate-based molecular materials[J].Chem.Rev.,1998.98:273-295.
[10]Rosenheim A,Bilecki R.Iso- and hetero-poly Acids.Ⅷ.Molybdic Acid Alkylarsinates[J].Berlin.Chem.Ber..1913,46:5.39-557.
[11]Du,Y.,Rheingold,A.L.,Maatta,E.A.A polyoxometalate incorporating an organoimido ligand:preparation and structure of[Mo_5O_(18)(MoNC_6H_4CH_3)~(2-)[J].Am.Chem.Soc.1992.114(11:345-346.
[12]Proust A.,Thouvenot R.,Chaussade M.,Robert F.,Gouzerh P.Phenylimido derivatives of[Mo_6O_(19)]~(2-)(?)syntheses.X-ray structures,cibrational,electrochemical.~(95)Mo and ~(14)N NMR studies[J].Inorg.Chim.Acta.1994,224(1-2):81-95.
[13]Clegg W.,R.Errington J.,Fraser K.A..Lax C..Richards D.G.In:Polyoxometalatcs:From Platonic Solids to Anti-Retroviral Activity,M.T.Pope.A.Muller(Eds.).Khlwer.Dordrecht.1994.352:113-115.
[14]Mohs T.R.Yap G.P.A..Rhcingold A.L..Maatta E.A..An Organoimido Derivative of the Hexatungstate Cluster:preparation and structure of[W_6O_(18)(NAr)]~(2-).(Ar=2.6-(i-Pr)_2C_6H_3)[J].lnorg.Chem.1995,34(1):9-10.
[15]Wu P.F.,Li Q.,Ge N.,Wei Y.G.,Wang Y.,Wang P.,Guo H.Y..An Easy Route to Monofunctionalized Organoimido Derivatives of the Lindqvist Hexamolybdate[J].Eur.J.Inorg.Chem.2004,268(14):2819-2822.
[16]Li Q.,Wu P.F..Wei Y.G.,Xia Y.,Wang Y.,Guo H.Y.,Orangic-inorganic hybrids:prcparation and structural characterization of(Bu_4N)_2[Mo_6O_(17)(NAr)_2]and(Bu_4N)_2[Mo_6O_(18)(NAr)](Ar=o-CH_3C_6H_4)[J].Z.Anorg.Allg.Chcm..2005.631:773-779.
[17]Xu.L,Lu.M,Xu.B.B..Wei Y.G.Peng Z.H.,Powell.D.R,Towards main-chain-polyoxometalate containing hybrid polymers:A highly efficient approach to bifunctionalized organoimido derivatives of hexamolybdates[J].Angew.Chem.Int.Ed.Engl.2002,41(21):4129-4132.
[18]Wei Y.G.,Lu.M..Cheung.C.F.C.,Barncs.C.L..Peng Z.H..Functionalization of[MoW_5O_(19)]~(2-)with aromatic aminesisynthesis of the first arylimido derivatives of mixed-metal polyoxometalates[J].lnorg.Chem,2001.40122):5489-5490.
[19]Wet Y.G.,Xu B.L..Barnes,Charles L.,Peng Z.H.,An efficient and convenient reaction protocol to organomido derivarises of polyoxometalates[J].Am.Chem.Soc,2001.123(27):4083-4084.
[20]Gouzerh.P.Proust.A.Main-Group Element.Organic,and Organomctallic Derivatives of Polyoxometalates[J].Chem.Rev.,1998,98:77-111.
[21]Xu.Bubin,Wei.Yongge,Barnes,Charles L.,Peng.Zhonghua.Hybrid molecular materials based on covalently linked inorganic polyoxometalates and organic conjugated systems[J].Angew.Chem.,Int.Ed.Engl..2001.40(12):2290-2292.
[22]Knoth W.H..Derivatives of heteropolyanions(?)Organic derivatives of W_(12)SiO_(40)~(4-).W_(12)PO_(40)~(3-).and Mo_(12)SiO_(40)~(4-)[J].Am.Chem.Soc.,1979,101(3):759-760.
[23]Xu B.B.,Wei Y.G.,Barnes C.L.,et al.Angew Chem.2001.113:2353-2354.
[24]魏永革.多酸类化合物的化学修饰-多钼-氧簇的氮配体官能团化,国家自然科学基金申请书,批准号:20201001.2002
[25]Raynaud M,Chermann J C,Plata F et al.C.R.Polyoxometalates in Medicine[J].Acad.Sci..Ser D.1971,272:347.
[26]胡长文.梁虹,王恩波.杂多峻的催化技术进展[J].现代化工.1992,(4):36
[27]王恩波.杂多酸催化剂连续法合成乙峻乙酯[J].催化学报.1993.14(2):147.
[28]吴通好.李建庆.杨洪茂,王国甲.两种结构钼磷酸的催化氧化行为[J].高等学校化学学报.1991.12(10):1378-1381.
[29]Yamase T.Fujita H.Fukushima K.Medical chemistry of polyoxometalales.Part Ⅰ.Potent antitumor activity of polyoxomolybdates on animal transplantable tumors[J].Inorg.Chem Acta.1988.151:15-18.
[30]Strong.JB..Yap.G.P.A.,Ostrander.R,Liable-sands.L.M..Rheingold.A.,Maatta.E.A.A New Class of Functionalized Polyoxometalates:Synthetic,Structural,Spectroscopic and Electrochemical Studies of Organoimido Derivatives of [Mo_6O_(19)]~(2-)[J].Am.Chem.Soc.2000.122(4):639-649.
[31]Proust A,Gouzerh P,Robert F.Molybdenum oxo nitrosyl complexes(?)Defeet Lindqvist compounds of the type [Mo_5O_(13)(OR)_4(NO)]~(3-)(R=CH_3,C_2H_5).Solid-state interactions with alkali-metal cations[J].Inorg.Chem.,1993.32(23):5291-5298.
[32]Chen Q,Salt J,Zubieta J,Synthesis and structural characterization of binuclear vanadium-oxo- organophosphonato complexes:building blocks for oxovanadium organophosphonate solids[J],Inorg.Chem.,1993.32(21):4485-4486.
[33]Tolkacheva E O.Popov K I.Dyatlova N.Phosphorus-~(31)NMR study of the complex formation in aqueous solutions of l-hydroxyethylenediphosphonic acid(H_5L)with molybdenum[Ⅵ)[J].Russ.Inorg.Chem..1992.37(7):1618-1625.
[34]Khan M I.Chen Q.Zubieta J.Oxomolybdenum(Ⅴ)potyanion clusters.Hydrothermal syntheses and structures of {(NH_4)_5Na_4{Na[Mo_6O_(12)(OH)_3(O_3PC_6H_5]_4}_2}·6H_2O(C_6H_5CH_2NMe_3)_4K_4{K_2[Mo_6O_(12)(OH)_3-(O_3PC_6H_5)_4]_2}·10H_2O and their relationship to the binuclear(Et_4N)[Mo_2O_4C_(13)(H_2O)_3]·5H_2[J].Inorg.Chem.Acta..1995,235(1-2):135-145.
[35]Ban S,Liu S.Shaikh S et aI.Molybdenum-95 NMR studies of taryldiazenido)- and torganohydra(?)do)molybd(?)es.Crystal and molecular structure of[n-Bu_4N]_3[Mo_6O_(18)(NC_6F_5][J].Inorg.Chem.,1988.27(20):3535-3543.
[36]J.T.,Rhule C.L.Hill,A.J.Deborah.Polyoxometalates in Medicine[J].Chem.Rev.1998.98(1):327-358.
[37]Lu M,Wei Y.G,Xu B,Cheung C.F.-C.,Peng Z.H,Powell D.Hybrid Molecular Dumbbells:Bridging Polyoxometalate Clusters with an Organic-Conjugated Rod[J].Angew.Chem.2002.41:1566-1568.
[38]Xu L,Lu M.Xu B.Wei Y.G,Peng,Z:Powell.D.R.Towards Main-Chain-Polyoxometatate-Containing(?)ybrid Polymers(?) Highly Efficient Approach to Bifunctionalizcd Organoimido Derivatives of Hexamolybdates[J]Angew Chem Int Ed.Engl,2003,41:4129-4132.
[39]Xu,B.B.Lu,M,Kang,J et al.Synthcsis and Optical Properties of Conjugated Polwners Containing Polyoxometalate Clusters as Side-Chain Pendants[J].Chcm.Mater.2005.17:2841-2851.
[40]Xu,B.B,Wei.Y.G.Barnes.C.L et al.Polyoxometalate composite Langmuir-Blodgett films:Preparation.struetural characterization and potential optoelectronic applications[J].Angew.Chem.2001,113:2353。
[41]Peng Z.H.Rational synthesis ofcovalently bonded organic-inorganic hydrids[J].Angew.Chem.Int.Ed.2004.43:930-935.
[42]Moore A.R,Kwen H.Beatty A.M,Maatta E.A.Organoimido-polyoxometalates as polymer pendants[J].Chem.Commun.2000:1793-1794.
[43]史亚鹏.有机基团取代的多钼氧酸盐的合成、结构及性质研究[D].西安:西北大学.2006.
[44]夏芸.新型多金属氧簇有机-无机分子基杂化化合物-六钼酸盐的有机亚胺衍生物的研究[D].北京:北京化工大学.2005.
[45]李强.魏永革,王远.郭洪猷.多酸有机亚胺衍生物的紫外-可见光谱及其取代基效应[J].光谱学与光谱分析,2005,25(6):923-926.
[46]田丹碧.仪器分析[M].北京:化学工业出版版社.2004
[47]夏芸,魏永革,郭洪猷.单取代多金属氧酸盐有机亚胺衍生物(n-Bu_4N)_2[Mo_6O_(18)(≡NAr)](Ar=o-CH_3OC_6H_4)的合成[J].化学学报,2005,63(20):1931-1935.
[48]荣国斌.波谱数据表-有机化合物的结构解析[M].上海:华东理工大学出版社.2000.
[49]李强.多酸有机亚胺衍生物的合成、结构与性能研究[D].北京:北京化工大学.2005.