通过有机配体界定的锌的磷酸化合物拓扑结构(晶

NovelZincPhosphateTopologiesDefinedbyOrganicLigands

JianFanandBrianE.Hanson*

DepartmentofChemistry,VirginiaPolytechnicInstituteandStateUniVersity,Blacksburg,Virginia24061

ReceivedMarch1,2005

Sixnewzincphosphates[C18H20N4][Zn4(HPO4)4(H2PO4)2(C18H18N4)3] 2H2O(1),[Zn4(HPO4)4(C18H18N4)3] 4H2O(2),[Zn3(HPO4)3(H2PO4)(C22H22N8)0.5(C22H24N8)0.5](3),[Zn2(HPO4)2(C18H16N4)](4),[Zn(HPO4)(C18H14N2)](5),and[Zn2-(HPO4)2(C12H10N4)](6)havebeensynthesizedundermildhydrothermalconditionsinthepresenceof1,4-bis(N-benzimidazolyl)butane(L1),1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene(L2),1,4-bis(imidazol-1-ylmethyl)naphthalene(L3),9-(imidazol-1-ylmethyl)anthracene(L4),and1,4-bis(1-imidazolyl)benzene(L5),respectively,pound2,alsoformedfromL1,pound3,preparedfromL2,possessesanunusualone-dimensionalframework,whichiscomposedofvertex-sharing4-ringsandtriplefused4-rings.Theinorganicportionsof4,5,and6eachadoptalayerstructure.Thesheetsin4and5havea4.82topology,andin6,a63topologyisobserved.Thezincatomsincompounds1 6arealltetrahedrallycoordinatedbyacombinationofphosphategroupsandorganicligands.Potentialrelationshipsbetweentheinorganicmotifsreportedinthepresentstudyareidentified.Theseareindicativeofapossiblepatternofself-assemblyofzincandphosphorustetrahedraandindicativeoftheroleoftheorganicligandsintheformationofhybridstructures.

Introduction

Frameworkzincmaterialsincludingzincphosphatesareofconsiderableinterestduetotheirwideapplicationintheareasofseparation,catalysis,andabsorption.1Thesynthesisofzincphosphateswithzero-,one-,two-,andthree-dimensional(3D)structureshasbeensuccessfullyachievedduringthepastdecade.2,3Twocommonlyobservedfeatures

*Towhomcorrespondenceshouldbeaddressed.E-mail:hanson@vt.edu.

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oftheobservedstructuresarethattheinorganicframeworksareoftenanionicandaprotonatedorganicamine,usedasatemplatingagent,directsthestructureformationbyfillingthevoidspaceandinteractingwiththeframeworkwithmultipointN-H Of(f)framework)hydrogenbonds.4Forexample,Raoandco-workersdevelopedasimpleuniversalrouteinwhichthereactionofaminephosphateandmetalionsyieldsahierarchyoftemplatedstructures.2bFurther,itisobservedthatphosphorusgroupsmodifiedbyorganicunitsareveryeffectiveintheconstructionofhybridmaterials.5Untilrecently,hybridzincphosphates/phosphitesthatcontaindirectZn-Nbondshavebeenrarelyreported.6Inthesecases,theorganicgroupscoordinatetothemetalionsoftheframeworkandactasstructure-buildingunits.Harrison,forexample,reportedR-and -ZnHPO3 N4C2H4asthefirstorganicallymodifiedzincphosphites.6aTheligands2,2′-dipyridine7andimidazoles6c,8havealsobeenreportedto

(4)Gordon,L.E.;Harrison,W.T.A.Inorg.Chem.2004,43,1808.(5)Shi,X.;Zhu,G.;Qiu,S.;Huang,K.;Yu,J.;Xu,R.Angew.Chem.,

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6998InorganicChemistry,Vol.44,No.20,2005

10.1021/ic050314tCCC:$30.25©2005AmericanChemicalSociety

PublishedonWeb09/10/2005