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Structure and Bonding 157 Series Editor: D.M.P. Mingos Banglin Chen Guodong Qian Editors Metal-Organic Frameworks for Photonics Applications 157 Structure and Bonding Series Editor: D.M.P. Mingos, Oxford, United Kingdom Editorial Board: F.A. Armstrong, Oxford, United Kingdom X. Duan, Beijing, China L.H. Gade, Heidelberg, Germany K.R. Poeppelmeier, Evanston, IL, USA G. Parkin, NewYork, USA M. Takano, Kyoto, Japan Forfurthervolumes: http://www.springer.com/series/430 Aims and Scope The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entirePeriodicTableandaddressesstructureandbondingissuesassociatedwithallof the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physicalandspectroscopictechniquesusedtodetermine,examineandmodelstruc- turesfallwithinthepurviewofStructureandBondingtotheextentthatthefocusison the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processesarealsorelevant Theindividualvolumesintheseriesarethematic.Thegoalofeachvolumeistogive thereader,whetheratauniversityorinindustry,acomprehensiveoverviewofanarea where new insights are emergingthat are ofinteresttoa larger scientific audience. Thuseachreviewwithinthe volumecriticallysurveys one aspectofthattopic and placesitwithinthecontextofthevolumeasawhole.Themostsignificantdevelop- mentsofthelast5to10yearsshouldbepresentedusingselectedexamplestoillustrate the principles discussed. A description of the physical basis of the experimental techniquesthathavebeenusedtoprovidetheprimarydatamayalsobeappropriate, ifithasnotbeencoveredindetailelsewhere.Thecoverageneednotbeexhaustivein data, but should rather be conceptual, concentrating on the new principles being developed thatwillallow the reader, who isnot a specialist in the areacovered,to understandthedatapresented.Discussionofpossiblefutureresearchdirectionsinthe areaiswelcomed. Reviewarticlesfortheindividualvolumesareinvitedbythevolumeeditors. In references Structure and Bonding is abbreviated Struct Bond and is cited as a journal. Banglin Chen Guodong Qian l Editors Metal-Organic Frameworks for Photonics Applications With contributions by B. Chen X.-M. Chen Y. Cui S. Du P. Falcaro l l l l l S. Furukawa K. Hirai S. Kitagawa W. Lin l l l l R. Medishetty G. Qian J.J. Vittal H. Zhang l l l l J.-P. Zhang T. Zhang l Editors BanglinChen GuodongQian DepartmentofChemistry Dpt.ofMaterialsScience&Engineering UniversityofTexasatSanAntonio ZhejiangUniversity SanAntonio Hangzhou Texas People’sRepublicofChina USA ISSN0081-5993 ISSN1616-8550(electronic) ISBN978-3-642-44966-6 ISBN978-3-642-44967-3(eBook) DOI10.1007/978-3-642-44967-3 SpringerHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2014931514 #Springer-VerlagBerlinHeidelberg2014 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe Publisher’s location, in its current version, and permission for use must always be obtained from Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter. ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface Photonics, the science of light emission, transmission, modulation, manipulation, and detection, are playing an essential role in many fields, including information processing,communication technologies,military, andbiomedicine.Comparedto electronics, photonics enable the transport and processing of information at the speedoflight.Thepresentboominopticalfibertechnologyisanexcellentexample ofhowmuchimpactphotonicshasontheadvancementofoursociety.Uptonow, variousinorganicandorganicmaterialshavebeenwidelydevelopedforphotonics applications, including nonlinear optical materials, luminescent materials, laser materials, photoactive materials, photoconductors, and so on. The research on the photonicsmaterialscombinestheappliedresearchofchemistry,solidstatephysics, materials science, and optical and computer engineering and will be the most dominatingforcesinvariousfieldsofscienceandengineering. Currently,metal-organicframeworks(MOFs)arebeingintensivelystudiedasa novelclassofhybridinorganic–organicmaterialwithultrahighporosity,enormous internal surface areas, together with the extraordinary tailorability of structure, dimension,size,andshape.Althoughthe photonicsapplication ofMOFmaterials isstillattheearlystagecomparedwiththeapplicationforgasstorage,separation, and heterogeneous catalysis, the currently available results have unambiguously demonstratedthatthedesignandconstructionofMOFsforphotonicsfunctionality is very active. Because of the inherent advantages of both organic links (easily modify,flexibility,versatility,etc.)andinorganicmetalions(uniqueelectronicand opticalnature),MOFswillopenalandofpromisingapplicationsinphotonicsfields whereconventionalinorganicororganicmaterialsmightnotbesuitable.TheMOF approach can also offer a variety of other attractive characteristics such as the straightforward syntheses, predictable structures and porosities, and collaborative propertiestodevelopnewphotonicsmaterialsandimportantapplications. DuetotheimportanceaswellastherapidprogressoftheMOFmaterialsinthe field of photonics, it is quite appropriate to publish this first book on MOFs for photonicsapplication.Thebookpresentsthemostup-to-datesourceofinformation on photonics applications of MOFs and not covered yet by other books. In this v vi Preface book,thedatabaseofphotonicsMOFs,thedesignprinciples,theuniquecharacter- isticsofMOFs,andthepotentialphotonicsapplicationsarediscussedindetail.The resultsobtainedinthelastyearsbythemainleadingMOFresearchersalloverthe worldarepresentedinthisbook,thusprovidingavalidandpreciousoverviewon the last developments and moreover on the future innovative applications of the MOFmaterialsinthefieldofphotonicsforscientistsworkinginthisarea. The book is organized in six chapters and opens with a chapter titled “Design and Construction of Metal-Organic Frameworks” by Chen and Zhang, which reviewsthefundamentalcharacteristics,moleculardesign,andsyntheticstrategies of MOFs. The chapter titled “Luminescent Properties and Applications of Metal- Organic Frameworks” by Qian et al. elaborates on the luminescent behavior of MOFsanddescribestheapplicationsofluminescentMOFsinthefieldsoflighting- emitting,chemicalsensors,andmedicine.Inchaptertitled“Metal-OrganicFrame- worksforPhotocatalysis”byLindiscussesthephotocatalysisapplicationofMOF materials.Vitaletal.thendescribethephotochemicaltransformationwithinMOFs in chapter titled “Photochemical Transformation within Metal-Organic Frame- works”. The chapter titled “Metal-Organic Frameworks for Nonlinear Optics” by Duetal.providesacomprehensivereviewofMOFsthatdisplaynonlinearoptical properties. Lastly, Furukawa and coworkers in chapter titled “Host-Guest Metal- Organic Frameworks for Photonics” describe the luminescent properties of host- guestMOFsandtheirpotentialapplicationsassensingmaterials. SanAntonio,TX,USA BanglinChen Hangzhou,People’sRepublicofChina GuodongQian Contents Metal–OrganicFrameworks:FromDesigntoMaterials ................... 1 Jie-PengZhangandXiao-MingChen LuminescentPropertiesandApplicationsofMetal-Organic Frameworks ................................................................... 27 YuanjingCui,BanglinChen,andGuodongQian Metal-OrganicFrameworksforPhotocatalysis ............................ 89 TengZhangandWenbinLin Metal-OrganicFrameworksforPhotochemicalReactions ............... 105 RaghavenderMedishettyandJagadeseJ.Vittal Metal–OrganicFrameworksforSecond-OrderNonlinearOptics ....... 145 ShaowuDuandHuabinZhang Host–GuestMetal–OrganicFrameworksforPhotonics .................. 167 KenjiHirai,PaoloFalcaro,SusumuKitagawa,andShuheiFurukawa Index .......................................................................... 187 vii StructBond(2014)157:1–26 DOI:10.1007/430_2013_100 #Springer-VerlagBerlinHeidelberg2013 Publishedonline:4May2013 Metal–Organic Frameworks: From Design to Materials Jie-PengZhangandXiao-MingChen Abstract Metal–organicframeworksareanewclassofadvancedporousmaterials, whichhaveseveralimportantcharacteristics,suchashighlyperiodical,diverseand designablestructures,highporosity,uniqueandmodifiableporesurface,aswellas framework flexibility. In this chapter, we give a brief account focusing on the molecular design, synthetic strategies and interesting properties and applications ofmetal–organicframeworkswithanumberofselectedexamples. Keywords Application (cid:1) Metal–organic framework (cid:1) Molecular design (cid:1) Porous coordinationpolymer(cid:1)Property(cid:1)Synthesis Contents 1 Introduction................................................................................... 2 2 DesignandTopology......................................................................... 3 2.1 Cluster-BasedFrameworks............................................................. 5 2.2 FrameworkInterpenetration............................................................ 8 3 Synthesis...................................................................................... 12 4 PropertiesandApplications.................................................................. 14 4.1 FrameworkFlexibility.................................................................. 15 4.2 GasStorage............................................................................. 16 4.3 SeparationandEnrichment............................................................ 19 4.4 MolecularSensing...................................................................... 21 5 Conclusions................................................................................... 22 References........................................................................................ 23 J.-P.Zhang(*)andX.-M.Chen MOEKeyLaboratoryofBioinorganicandSyntheticChemistry,SchoolofChemistryand ChemicalEngineering,SunYat-SenUniversity,Guangzhou510275,China e-mail:[email protected];[email protected] 2 J.-P.ZhangandX.-M.Chen 1 Introduction Althoughthetermcoordinationpolymerfirstappearedin1960s,andcanbetracedup tothefirstman-madecoordinationpolymerorPrussianBluebyanaccidentinearly eighteenthcentury,theveryextensiveinterestincoordinationpolymerswastriggered by several pioneering reports on discoveries of the porous structures and related functionalities around 1990. In particular, Robson et al. reported the porous metal cyanideswithion-exchangeproperties[1,2],Kitagawaetal.demonstratedmethane adsorptioninamicroporouscoordinationpolymer[3],andYaghietal.reportedarich familyofhighlyporousandthermallystablemetalcarboxylates[4]thatweretermed metal–organic frameworks (MOFs) [5]. The research in coordination polymers has grownsubstantiallyinthepastdecade,asbeingevidencedbytheexponentialincrease ofpublicationnumber. MOFsareconstructedbymetalions/clustersandorganicbridgingmolecules.They canberegardedasasubclassofcoordinationpolymers,sincethemetalions/clusters should be solely bridged by organic molecules (or ligands) via coordination into two-dimensional (2D) or three-dimensional (3D) porous networks in MOFs [5], whereas the bridging ligands may be either inorganic or organic in coordination polymers[6].Nevertheless,thetermMOFhasbeenverypopularlyusedfordifferent types of coordination compounds with 3D to 1D, and even 0D, both porous and nonporous structures. Anyway, we refer MOF to porous coordination polymer in thischapter. MOFsmayhavebothadvantagesofinorganicandorganicmaterials[7,8],buttheir physicalandchemicalstabilitiesarerelativelylowerthanthoseofcarbonmaterials and inorganic zeolites solely composed of carbon–carbon and metal-oxide bonds, respectively.Asbeingwellknownthatmetalions(orclusters)andorganicbridging ligands are diversified in coordination behavior and geometry, the combinations of metalions(orclusters)andbridgingorganicligandsthroughcoordinationinteractions are almost infinite. Consequently, a huge number of MOFs with different functionalities, such as gas adsorption, separation, sensing, catalysis, and lumine- scence,havebeendocumented.MOFshavesomeimportantcharacteristicsowingto their unique compositions and structures, such as highly periodical structures, high porosity,specialandmodifiableporesurface,aswellasframeworkflexibility.The3D periodicityorcrystallinitybenefitsthedeterminationoftheirstructures,inparticular bysingle-crystalX-raydiffraction,whichisfundamentalforawellunderstandingof thestructure–propertyrelationshipandbetterdesignofnewmaterials.Highporosity canberationallyachievedbyusingsuitableframeworkstructureand/orlongorganic ligands,whichisimportantforadsorptionandstorageofmolecules,catalysis,etc.The poresurfaceofMOFisdecoratedbybothinorganicmoietiesandvariousfunctional groupsoforganicligands,whichcanbereadilytailoredtomeetaspecificpropertyor function, such as selective adsorption, separation, and sensing. Compared to the traditionalzeolitesandotherinorganicporousmaterials,MOFsareveryuniquefor their highly flexible host framework structures, which are very useful for smart materialswithspecialsorption,storage,separation,andsensingproperties[9].