酪氨酸修飾的金屬Corrole化合物的合成和性能研究.pdf

1、大連理工大學碩士學位論文酪氨酸修飾的金屬Crole化合物的合成和性能研究姓名：夏鳴申請學位級別：碩士專業(yè)：應(yīng)用化學指導教師：劉建輝20070601酪氨酸修飾的金屬Corrole化合物的合成和性能研究SynthesisandPropertiesofMetalCorroleComplexesModifiedbyTyrosineAbstractThefourelectronoxidationofwaterinphotosyntheticorg

2、anismsisachievedbyanoxygenevolvingcomplex(OEC)inphotosynthesis，whichisoneofthemostfimdamentalchemicalprocessesinnatureAseriesofXraystructureanalysisofphotosystemII(PSⅡ)indicatedthattheactivesiteinaphotosyntheticOECprotei

3、ncontainsaMmCaclusterandaneighboringtyrosinefryrz)islinkedbetweenP6soandOECBylightabsorptionoftheprimaryelectrondonorP鴣oconsistingofehlorophyll4molecules，electrontransferoccursfromtheexcitedP6s0toaprimaryelectronaccepter

4、pheophytinandsubsequentlytotwoquininesformingP680radicalcationThephotooxidizedP6setrievestheelectronfromaM114CaclusterviaTyr=Afterfourphoto—processes，twomeleeularwaterareoxidizedtoamolecularoxygenTyrziscrucialforstabiliz

5、ationoftheprimarychargeseparationAstoelectrondonoroxidationofwaterattheMmCaclusteroccmsinfivestepsandinvolvessixoxidationstates(So—S4)Thoughthemechanismofdioxygenevolutionhasnotbeendeterminedcompletely，thestageofoxygenev

6、olutionwouldinvolveahighvalentmanganesespeciesHowtoobtainastableligandtostablehi幽valentmanganeseisstillaurgentproblem，Corrolesalealomatictetrapyrrolemacrocyclesasaringcontractedanalogueofpurphyfinswhichhavebeenprovedtost

7、abilizelligheroxidationstatesforcoordinatedmetalscomparetothemorefamousporphyrinsTherefore，theligand4whichcontainsacorroleandatyrosineconnotedthrough姐amidebondwasdesignedaswellasitsMacomplex4bforthestudyofwateroxidationT

8、hesynthesisstartsfromadipyrromethanecompound1preparedaccordingtotheliteratureAfterthreestepsofcorroleformationreductionofthenitrogroupin2andformationofamidobondbyDCC，thealTnedcorrolecompound4issynthesizedAsubsequentmetal

9、ionseomplexationgivescorrespondingcomplexes4aand4bThecoppercomplexes2aand3aoftheintermediates2and3werealsopreparedforcomparisonMostofsevennewcomplexesatecharacterizedby‘HNM＆MS，UV一講s，mass—spectrometryelementalanalysisThro

10、ughthemeasurementsofMS，UV州s，thevalencestateforthecentralmetalionofmanganesecomplexes4bisconfirmed幻beMn(I、，)。Theemissionpropertyinstatesthattheemissionofligands2and3isstrong，butnoemissionisobservedfor協(xié)由metalcomplexduetoth