TEMPERATURE DEPENDENCE OF THE FLUORESCENCE SPECTRA OF LADDERLIKE POLYPHENYLSILSESQUIOXANE AND LADDERLIKE 1,4- PHENYLENE-BRIDGED POLYVINYLSILOXANE

(整期优先)网络出版时间:2002-01-11
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Fluorescencespectraofladderlikepolyphenylsilsesquioxane(LPPS)andladderlike1,4-phenylene-bridgedpolyvinylsiloxane(LPPVS)havebeenmeasuredasafunctionoftemperature(4-55℃),indilutetetrahydrofuransolution.Theexcimer(IE)tomonomer(IM)intensityratio(IE/IM)ofLPPSdilutesolutionshowsadoublelinearArrheniusplotwithabreakpointascribabletoatransitiontemperatureTr.Thisbehaviorhasnotbeenfoundforsinglechainpolyorganosiloxanes.WhenIn/EofLPPSwasplottedagainst1/T,italsogaveadoublelinearplotwithonebreakpoint,whichwasfoundinsinglechainpolyorganosiloxanes.ThedifferentbehaviorsbetweenLPPSandsinglechainpolyorganosiloxanesmaybemainlyattributedtotherelativelyrigiddouble-chainmacromolecularbackboneofLPPS.However,theln(IE/IM)ofdiluteLPPVSsolutionversus1/Tshowsasimplelinearvariationwithapositiveslopewhichconfirmsourproposition.ThedifferencebetweenthefluorescenceresultsofLPPSandthoseofLPPVSmaypossiblyderivefromtheirstructuredifferencesandcooperativemotioninbackbonechainbonds.