超分子金属凝胶

22620106PROGRESSINCHEMISTRYVol.22No.6Jun.20102009720099*No.2057404120874055863No.2009AA062903[e-mail]*100084/。。、、。、、。O641.3O631A1005-281X201006-1094-08SupramolecularMetallogelsChenKaiJinXinTangLimingLaboratoryofAdvancedMaterialsDepartmentofChemicalEngineeringTsinghuaUniversityBeijing100084ChinaAbstractSupramoleculargelshaveevolvedintoaclassofsmart/functionalnanomaterialswithextensiveapplicationpotentialsrecently.Mostsupramoleculargelsstudiedtodayemployhydrogenbondingormolecularstackingasthedrivingforceforgelation.Despitethemajorrolethatmetalcoordinationplaysinsupramolecularchemistrytheuseofmetal-ligandinteractionsintheareaofsupramoleculargelshasbeensomewhatneglecteduntilveryrecently.Supramoleculargelsincludingmetalionscancapitalizeontheuniquerichnessoftheattributesofmetalionssuchasphoto-electroniccatalyticredoxwhichstimulatesresearchinthisarea.Inthisreviewthebasicconceptsofmetallogelsarefirstgivenandthendetailedexamplesarepresentedtorelatethemolecularstructuresespeciallythecomplexinggroupsmetalionsusedtothepropertiesandfunctionsofthegelswhicharedividedintotwocategoriesgelatorbasedmetallogelsandcoordinationpolymergels.Moreoverabnormalgelationbehaviorsinmetallogelswillbebriefed.KeywordssupramolecularmetallogelcoordinationstructuresContents1Introduction2Definitionofsupramolecularmetallogel3Classificationofsupramolecularmetallogels3.1Metallogelsbasedongelators3.2Metallogelsbasedoncoordinationpolymers4Abnormalgelationbehaviorsofmetallogels5Conclusion16·1095·12/34。gelator15。、pH、。5。、pH6。7、8、9、1011。、12。1314。———。。、、。。2。。1000。-、。。。33.1。。。。1。15。216。。1713。3。·1096·22-。18。1-17Fig.1Cholesterol-appendedferrocenederivativesandthegelationbehaviorofsol-geltransitiontriggeredbychemicalredoxreaction17Shinkai19。4L。4Cu+CuⅠ·L2CuⅠ。CuⅠ。520。Cu、Pd、Pt3。PtⅡ-。、21—23。。Tam24Pt。26CF3SO－3DMSOba780nmPt-Ptπ-π-3MMLCT。-。2Pt6a、b24Fig.2PlatinumⅡterpyridylalkynylcomplexes6initstrifluoromethanesulfonatesaltandthegelaandsolutionbstatesof624。Camerel257。7FeⅡ2∶1。77RuⅡ。7FeClO42。FeClO42FeⅡ。26-Tu2626-6·1097·Pd。1PdPd。-1Pd28Scheme1Metallogelatorsbasedonbis-N-heterocycliccarbinepalladiumcomplexes28Cr27。8Pd-50℃。π-π、-。Tu28。9a9b。1011。9a9b。。Aida29AuⅠ12。12AuⅠ-AuⅠ254nm。--。30。21333Scheme2Pyridylderivative13anditscomplexwithAgⅠasagelator33。Yoon31。Bardelang32。33213。13AgSO3CF313AgⅠ2∶1。·1098·2234。3.2coordinationpolymer。-metal-organicframeworksMOFs35。Mirkin36—39。40。。。。。14。14AgBF441。Bu4N+F－F－Ag+Ag+。C2F5CO－2BF－4BF－4。。Ag+。Rowan424326--1′--4-515。152∶13∶195%5%。。44。16、1718、19PdⅡ。PdⅡ20PdⅡPdⅡPdⅡ。16、1720DMSO。PdOAc221PdOAc2。16PdOAc2DMSO17NNH。18216h201818。1920。6·1099·45。3223AgⅠ30s。NN′-。。332222AgNO345Fig.3Tripodalligand22containingthreepyridylgroupsandillustrationoftheprocessoffabricatingpolymernanotubestemplatedfrommetallogelsbasedon22andAgNO345。James46。3FeⅢ。Andrews47LaⅢ。Sijbesma48bolaRhⅠ、IrⅠ。。Weiss49FeⅢFeⅢ3FeⅢFeⅢ4。Ray50bola23CoCl2NiCl2。23。4FeⅢ49Fig.4TwopossiblearrangementsoftheFeⅢcomplexesbetweenphosphonateestersandtheFeⅢions494。。5Kimizuka5124、25Co2+·1100·22Co243Cl2a。0℃b。。CoⅡ。52425Co243Cl2ab51Fig.5Structureof124-triazoleligands2425bearinglongalkylchainandtheheat-setgelationbehaviorofthecomplexCo243Cl25162652Fig.6StructureofdinuclearPdcomplex26anditssonicationtriggeredgelationwithproposedmolecularpackingfashions52Naota52。Pdbola266。PdⅡ26。26π。Naota53Pd。5、。。。1EstroffLAHamiltonAD.Chem.Rev.20041041201—12182TerechPWeissRG.Chem.Rev.1997973133—31603SangeethaNMMaitraU.Chem.Soc.Rev.200534821—8364WangYJTangLMYuJ.ProgressinChemistry20092161312—13245MoriyamaMMizoshitaNYokotaTetal.Adv.Mater.2003151335—13386VanBommelKJCvanderPolCMuizebeltIetal.Angew.Chem.Int.Ed.2004431663—16677BhattacharyaSSrivastavaAPalA.Angew.Chem.Int.Ed.2006452934—29378DzolicZCamettiMCortADetal.Chem.Commun.20073535—35379KimHJLeeJHLeeM.Angew.Chem.Int.Ed.2005445810—581410StanleyCEClarkeNAndersonKMetal.Chem.Commun.20063199—320111MaedaHHaketaYNakanishiT.J.Am.Chem.Soc.200712913661—1367412LeeKYMooneyDJ.Chem.Rev.20011011869—187913LlusarMSanchezC.Chem.Mater.200820782—82014XiaYWangYChenKTangLM.Chem.Commun.20085113—511515HanabusaKMaesakaYSuzukiMetal.Chem.Lett.20006·1101·1168—116916SohnaJESFagesF.Chem.Commun.1997327—32817LiuJHePLFangYetal.Adv.Mater.2008202508—251118KlawonnTGansauerAWinklerIetal.Chem.Commun.20071894—189519KawanoSFujitaNShinkaiS.J.Am.Chem.Soc.20041268592—859320ShirakawaMFujitaNTaniTetal.Chem.Eur.J.2007134155—416221AndresPSchubertU.Adv.Mater.2004161043—106822FustinCAGuilletPSchubertUSetal.Adv.Mater.2007191665—167323HofmeierHSchubertUS.Chem.Soc.Rev.200433373—39924TamAYYWongKMCWangGXetal.Chem.Commun.20072028—203025CamerelFZiesselRDonnioBetal.NewJ.Chem.200630135—13926TuTAssenmacherWPeterlikHetal.Angew.Chem.Int.Ed.2007466368—637127BuhlerGFeitersMCNolteRJMetal.Angew.Chem.Int.Ed.2003422494—249728TuTBaoXLAssenmacherWetal.Chem.Eur.J.2009151853—186129KishimuraAYamashitaTAidaT.J.Am.Chem.Soc.2005127179—18330HuiJKHYuZMacLachlanMJ.Angew.Chem.Int.Ed.2007467980—798331YoonSKwonWJPiaoLetal.Langmuir2007238295—829832BardelangDCamerelFHotzeACGetal.Chem.Eur.J.2007139277—928533LiuQTWangYLWuLXetal.L