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1、PublishedonWeb03/06/2003DetectionofNitroaromaticExplosivesBasedonPhotoluminescentPolymersContainingMetallolesHonglaeSohn,MichaelJ.Sailor,*DouglasMagde,*andWilliamC.Trogler*ContributionfromtheDepartmentofChemistryandBiochemistry,UniVersityofCaliforniaatSanDiego,9500GilmanDriVe,San
2、Diego,California92093-0358ReceivedSeptember26,2002;E-mail:wct@chem.ucsd.eduAbstract:Thesynthesis,spectroscopiccharacterization,andfluorescencequenchingefficiencyofpolymersandcopolymerscontainingtetraphenylsiloleortetraphenylgermolewithSi-Si,Ge-Ge,andSi-Gebackbonesarereported.Poly
3、(tetraphenyl)germole,2,wassynthesizedfromthereductionofdichloro-(tetraphenyl)germolewith2equivsofLi.Silole-germolealternatingcopolymer3wassynthesizedbycouplingdilithiumsaltsoftetraphenylsiloledianionwithdichloro(tetraphenyl)germole.Othertetraphenylmetallole-silanecopolymers,4-12,
4、weresynthesizedthroughtheWurtz-typecouplingofthedilithiumsaltsofthetetraphenylmetalloledianionandcorrespondingdichloro(dialkyl)silanes.Themolecularweights(Mw)ofthesemetallole-silanecopolymersareintherangeof40006000.Detectionofnitroaromaticmolecules,suchasnitrobenzene(NB),2,4-din
5、itrotoluene(DNT),2,4,6-trinitrotoluene(TNT),andpicricacid(PA),hasbeenexplored.AlinearStern-Volmerrelationshipwasobservedforthefirstthreeanalytes,butnotforpicricacid.Fluorescencespectraofpolymetallolesormetallole-silanecopolymersobtainedineithertoluenesolutionsorthinpolymerfilmsdi
6、splayednoshiftinthemaximumoftheemissionwavelength.Thissuggeststhatthepolymetallolesormetallole-silanesexhibitneitherð-stackingofpolymerchainsnorexcimerformation.Fluorescencelifetimesofpolymetallolesandmetallole-silanesweremeasuredbothinthepresenceandabsenceofTNT,andôo/ôisinvarian
7、t.Thisrequiresthatphotoluminescencequenchingoccursbyastaticmechanism.Introductionnance,12energy-dispersiveX-raydiffraction,13neutronactivationanalysis,electroncapturedetection,5andcyclicvoltammetry.14Chemicalsensorsfornitroaromatics,1,2whichoffernewThesetechniquesarehighlyselecti
8、ve,butsomeareexpensiveapproachestotherap
