微波法合成席夫碱配合物

微波法合成席夫碱配合物

0py：普组合pyrace和3-amon2-自由基双环pyrace以碳氢化合金属丝的基本含量为证据，可通过运输到框架内的碳氢化合金属丝。a-司法模型的数量和特征、线性模件和菲涅耳的自由、轻敲和敏感行为，数量和特征的数量，生命的创造，生命的遗迹和遗迹，促进血液循环和转化。以轻碳颗粒、缓慢、缓慢和多环芳烃的非i类活动。本发明系统的传输系统采用微芯片管理系统和微芯片颗粒的传输系统。在several分配中，有一个部分被设计和开发的框架，并且可以通过母皮屑帝国马蹄莲的基本形态来确定。Microwave-assistedsynthesisisabranchofgreenchemistry.Theapplicationofmicrowave-assistedsynthesisinorganic,organometallicandcoordinationchemistrycontinuestodevelopatanastonishingpace.Microwaveirradiatedreactionsundersolvenfreeorlesssolventconditionsareattractiveinofferingreducedpollution,lowcostandhighyieldswithsimplicityinprocessingandhandling.Thesalienfeaturesofmicrowaveapproachareshorterreactiontimes,simplereactionconditionsandenhancementinyields.Inthispaper,wehavedescribedthesynthesisphysicochemicalcharacterizationandbiologicaactivitiesofCr髥,Co髤,Ni髤andCu髤complexeswithligandsderivedfrom5-chlorosalicylaldehydewith2-amino-5-nitrothiazole(L1H)and4-chlorobenzaldehydewith2-amino-3-hydroxypyridine(L2H)(Fig.1)Thereactionwascarriedoutbybothconventionalandmicrowavemethods.Thisligandsystemcoordinateswiththemetalionsinabidentatemannerthroughtheoxygenandazomethinenitrogen.Themetalcomplexesformedwiththesetwonewligandsmaybeusedasprecursorsforthesynthesisofnewcompounds.Someofthemmayexhibitinterestingphysicalandchemicalpropertiesandpotentiallyusefulbiologicalactivities.1u2004范围u200日起算价...4.3.4和.和..3.4和..3.4和....3.4和..............................................3.3.3AllthechemicalsandsolventsusedwereofARgrade.AllthereagentsusedforthepreparationoftheSchiffbaseswereobtainedfromSigma-Aldrich.MetalsaltswereobtainedfromLobaChemie.ElementalanalyseswereperformedonanElementalVarioELIIICarloErba1108analyzer.FAB-massspectrawererecordedonaJEOLSX102/DA6000MassSpectrometerusingargon/xenon(6kV,10mA)astheFABgas.Theacceleratingvoltagewas10kVandthespectrawererecordedatroomtemperature.Electronicspectra(inDMSO)wererecordedonPerkinElmerLambda-2B-spectrophotometer.Molarconductancemeasurementswereconductedusing10-3molL-1solutionofthecomplexesinDMSOonElico-CM82ConductivityBridgeatroomtemperature.MagneticsusceptibilitymeasurementswerecarriedoutonaGouybalanceatroomtemperatureusingHg[Co(SCN)4]asthecalibrant.FTIRspectrawererecordedusingKBrpelletonaPerkinElmerRX1spectrophotometerinwavenumberregionof4000～400cm-1.1HNMRspectrawererecordedonaJEOLAL300FTNMRspectrometeremployingTMSastheinternalreferenceandCDCL3asthesolvent.X-bandEPRspectrawererecordedonaVarianE-112spectrometeratroomtemperatureoperatingattheX-bandregionwith100kHzmodulationfrequency,5mWmicrowavepowerand1GmodulationamplitudeusingTCNEastheinternalstandard.Thermogravimetricanalysiswascarriedoutunderatmosphericconditionwithaheatingrateof10℃·min-1onTGAQ500UniversalV4.5ATAInstrument.PowderX-raydiffraction(XRD)patternswererecordedonaRINT2000wideanglegoniometer.ThesolidstateelectricalconductivityhasbeenmeasuredbyimpedancespectroscopicmethodusingHIOKI3532-50LCRHitester.Microwaveassistedsynthesiswerecarriedoutinopenglassvesselonamodifiedmicrowaveovenmodel2001ETBwithrotatingtrayandapowersourceof230Vmicrowaveenergyoutputof800Wandmicrowavefrequencyof2450MHz.Athermocoupledeviceusedtomonitorthetemperatureinsidethevesselofthemicrowave.Themicrowavereactionswereperformedusingon/offcyclingtocontrolthetemperature.1.1双标so岩使用so岩so条件方菌株共同反应价TheinvitrobiologicalactivityoftheinvestigatedSchiffbaseanditsmetalcomplexeswastestedagainsthebacteriaEscherichiacoliandStaphylococcusaureusbydiscdiffusionmethodusingnutrientagarasthemediumandstreptomycinasthecontrol.TheantifungalactivitiesofthecompoundswerealsotestedbytheWelldiffusionmethodagainstthefungAspergillusnigerandCandidaalbicans,onpotatodextroseagarasthemediumandmiconazoleasthecontrol.EachofthecompoundswasdissolvedinDMSOandsolutionswiththeconcentrationof25,50and100mg·L-1werepreparedseparately.Inatypicaprocedure,awellwasmadeonagarmediuminoculatedwithmicroorganism.Thewellwasfilledwiththetestsolutionusingamicropipetteandtheplatewasincubated24hforbacteriaat37℃and72hforfungiat30℃.Duringthisperiod,thetessolutiondiffusedandthegrowthoftheinoculatedmicroorganismwasaffected.Theinhibitionzonewasdeveloped,atwhichtheconcentrationwasnoted.1.2-am采用2-amwell,3,4h,3,4h,3,4h,3,4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4.4h,3.4h,3.4h,3.4h,.4.3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3.4h,3TheSchiffbaseshavebeensynthesizedbythecondensationofequimolarratioof5-chlorosalicylaldehydewith2-amino-5-nitrothiazoleand4-chlorobenzaldehydewith2-amino-3-hydroxypyridinedissolvedinethanol.Theresultingreactionmixturewasstirredwell,refluxedfor3～4handthenallowedtocoolovernight.ThecolouredsolidprecipitateoSchiffbaseobtainedwasfiltered,washedwithcoldethanolseveraltimesanddriedunderreducedpressureinadesiccator.ThepurityofthesynthesizedcompoundswascheckedbyTLCusingsilicagelG(yield:72.5%～75.0%).1.3rectityinagrangeb.案例Theequimolar(1∶1)ratioof5-chlorosalicylaldehydewith2-amino-5-nitrothiazoleand4-chlorobenzaldehyde(L1H)with2-amino-3-hydroxypyridineweremixedthoroughlyinagrinder.Thereactionmixturewasthenirradiatedbythemicrowaveovenbytaking3～4mLsolvent.Thereactionwascompletedinashorttime(4～5min)withhigheryields.TheresultingproductwasthenrecrystallizedwithethanolandfinallydriedunderreducedpressureoveranhydrousCaCl2inadesiccator.TheprogressofthereactionandpurityotheproductwasmonitoredbyTLCusingsilicagelG(yield:85.4%～87.0%).1.4anolicsoctgratio.thill-reclusin12金属ligadratio...................3.4和........................................3.3.3.Themetalcomplexes(Fig.2and3)havebeenpreparedbymixing50mLethanolicsolutionoCrCl3·6H2O/CoCl2·6H2O/NiCl2·6H2O/CuCl2·2H2Owith50mLethanolicsolutionofSchiffbases(L1H/L2H)in1∶2(metal∶ligand)ratio.Theresultingmixturewasrefluxedonwaterbathfor6～10h.AcolouredproducappearedonstandingandcoolingtheabovesolutionTheprecipitatedcomplexwasfiltered,washedwithetherandrecrystallizedwithethanolseveraltimesanddriedunderthereducedpressureoveranhydrousCaCl2inadesiccator.Itwasfurtherdriedinelectricovenat50～70℃(yield:59.5%～70.1%).1.5方法Theligandandthemetalsaltsweremixedin1∶2(metal∶ligand)ratioinagrinder.Thereactionmixturewasthenirradiatedbythemicrowaveovenbytaking3～5mLsolvent.Thereactionwascompletedinashorttime(7～10min)withhigheryields.TheresultingproductwasthenrecrystallizedwithethanolandetherandfinallydriedunderreducedpressureoveranhydrousCaCl2inadesiccator.TheprogressofthereactionandpurityoftheproductwasmonitoredbyTLCusingsilicagelG(yield:78.0%～84.3%).2国际习惯法国际习惯法.日非paracketolgecolix..3.3.3日非paracketolgecolix...........3.3日起保护solidssolidmethodssolixmethodssolixmethodssolixmethodsAsaresultofmicrowaveassistedsynthesis,itwasobservedthatthereactionwascompletedinashorttimewithhigheryieldscomparedtotheconventionalmethod.Inthemicrowavemethodhomogeneityofthereactionmixturewasincreasedbytherotatingofreactionplatformtray.Theconfirmingoftheresultswasalsocheckedbytherepeatingofthesynthesisprocess.Comparativestudyresultsobtainedbymicrowaveassistedsynthesisversusconventionaheatingmethodisthatsomereactionsrequired3.2～9.2hbyconventionalmethodwascompletedwithin4.1～9.4min.bythemicrowaveirradiationtechniqueyieldshavebeenimprovedfrom59.5%～75.0%to78.0%～87.0%.Allthemetalcomplexesarecoloured,solidandstabletowardsairandmoistureatroomtemperatureTheydecomposeonheatingathightemperature,andaremoreorlesssolubleincommonorganicsolventsThecomparativeresultsofconventionalandmicrowavemethodsandanalyticaldataofthecompounds,togetherwiththeirphysicalpropertiesconsistentwithproposedmolecularformulaandmagneticmomentvalues,aregiveninTable1.Allthemetalchelateshave1∶2(metal∶ligand)stoichiometryTheobservedmolarconductanceofthecomplexesinDMSOatroomtemperatureareconsistentwiththenon-electrolyticnatureofthecomplexesexceptCr髥complexofboththeSchiffbaseligands,whichwaselectrolyticnature.CM=Conventionalmethod,MM=Microwavemethod.2.1eunthiercopo3s1heth3mequeTheFAB-massspectrasuggestthatallthecomplexeshaveamonomericnature.Thesecomplexesshowmolecularionpeaksingoodagreementwiththeempiricalformulasuggestedbyelementalanalyses.TheFABmassspectraoftheligand(L1H)andits[Co(L1)2(H2O)2]complex,and(L2H)andits[Co(L2)2(H2O)2]complexwererecordedandtheyareusedtocomparetheirstoichiometrycomposition.TheSchiffbases(L1H)and(L2H)showamolecularionpeakatm/z285and230respectively.The[Co(L1)2(H2O)2]and[Co(L2)2(H2O)2]complexshowsamolecularionpeakatm/z662and560,respectively,confirmingthestoichiometryofSchiffbasesandthiercomplexesasML2type.Itisingoodagreementwiththemicroanalyticaldata.2.21H-NMRspectra1H-NMRspectraoftheSchiffbaseswererecordedinCDCL3solutionusingTMSastheinternalstandardThe1H-NMRspectraoftheL1Hligandshowsthesignaat7.250～7.668ppm(m)foraromaticproton,6.986ppm(s)forthiazoleprotonand9.228ppm(s)forazomethineproton.Thepeakat12.279(s)isattributedtothephenolic-OHgroup,disappeareduponshakenofD2OThe1H-NMRspectraoftheL2Hligandshowsthesignaat6.992～7.632ppm(m)foraromaticprotonand8.783ppm(s)forazomethineproton.Thepeakat10.262ppm(s)isattributedto-OHgrouppresentinpyridinemoiety,disappeareduponadditionofD2O.2.3ywellingensiphenolizacts关于cor-1,3,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,3,4,4,3,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,3,4,4,4,4,3,4,4,4,4,3,4,4,4,3,4,3,4,4,4,4,3,4,4,3,4,4,3,4,4,4,4,4,4,4,4,4,4,4,3,4,4,4,4,4,4,4,3,4,4,4,3,4,4,3,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,3,4,4,4,4,4,4,4,4,4,4,3,4,4,4,4,4,4,4,4,3,4,3,4,3,4,4,4,3,4,3,4,4,3,4,4,3,4,3,4,3,4,4,4,3,4,3,4,3,4,4,3,4,4,4,3,4,4,3,4,4,4,4,3,4,4,4,4,4,4,3,4,4,3,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4,4ThedataoftheIRspectraofSchiffbaseligandanditsmetalcomplexesarelistedinTable2.TheIRspectraofthecomplexesarecomparedwiththoseofthefreeligandinordertodeterminetheinvolvementofcoordinationsitesinchelation.Characteristicpeaksinthespectraoftheligandandcomplexesareconsideredandcompared.IRspectraoftheL1Hligandexhibitthemostcharacteristicbandsat3302cm-1ν(O-H),1637cm-1ν(C=N,azomethine),1562cm-1ν(C=N,thiazole),1258cm-1ν(C-O)and754cm-1ν(C-S-C).TheformationofSchiffbase,5-chlorosalicylidene-2-amino-5-nitrothiazoleisnotedfromtheabsenceofC=OandNH2peaksintheligand.Allthemetalcomplexesshowabroadbandat3374～3419cm-1whichmaybeduetostr(OH).Amediumintensitybandat814and805cm-1suggeststhepresenceofcoordinatedwaterinCr髥andCo髤.Thebandat1637cm-1duetotheazomethinegroupoftheSchiffbasehasshiftedtolowerfrequency(1602～1612cm-1)aftercomplexation,indicatingthebondingofnitrogenoftheazomethinegrouptothemetalionandthiscanbeexplainedbythedonationofelectronsfromnitrogentotheemptyd-orbitalofthemetalatom.ThephenolicC-Ostretchingvibrationappearedat1258cm-1inSchiffbaseshiftstowardshigherfrequencies(23～40cm-1)inthecomplexes.ThisshiftconfirmstheparticipationofoxygenintheC-O-Mbond.Thenewbandsat550～564cm-1and486～496cm-1havebeenassignedtoM-OandM-Nmodes,respectively.Theν(C=N)at1563cm-1andν(C-S-C)at754cm-1ofthethiazoleringremainunchanged,suggestingthatthiazolegroupdoesnotcoordinatetometalbyneithernitrogennorsulpheratom.IRspectraoftheL2Hligandexhibitthemostcharacteristicbandsat3280cm-1ν(O-H),1625cm-1ν(C=N,azomethine)and1480cm-1ν(C=N,pyridine)TheformationofSchiffbase,4-chlorobenzylidene-2-amino-3-hydroxypyridine,isnotedfromtheabsenceofC=OandNH2peaksintheligand.Allthemetalcomplexesshowabroadbandat(3342～3384cm-1)whichmaybeduetoνstr(OH).Amediumintensitybandat789cm-1,812cm-1and800cm-1inCr髥,Co髤andCu髤,respectively,suggeststhepresenceofcoordinatedwaterinthesecomplexes.ButthisbandisnotpresentedintheNi髤complex,indicatingthattheabsenceofcoordinatedwatermoleculesinNi髤complex.Theband1625cm-1duetotheazomethinegroupoftheSchiffbasehasshiftedtolowerfrequency(1598～1605cm-1)aftercomplexation.Thisindicatestheinvolvementofazomethinenitrogentothemetalion.IntheIRspectraofthecomplexes,thestretchingvibrationofthefreeligandν(O-H)3280cm-1isnotobserved,suggestingdeprotonationofthehydroxylgroupandformationofM-Obonds.Inthelowfrequencyregion,thebandofweakintensityobservedforthecomplexesintheregion517～528cm-1isattributedto(M-O)andintheregion482～491cm-1to(M-N).Theν(C=N)at1480cm-1inligand,thereisnoappreciablechangeinthecomplexesspectrumwhichindicatesthatthepyridineringnitrogendoesnotparticipateincoordination.TheIRdataofboththeSchiffbaseanditsmetalcomplexesshowthattheSchiffbases(L1HandL2H)behaveasbidentatesandarebondedtothemetalionthroughoxygenandiminonitrogenofazomethinegroup.2.4yhabeensecopercesrespity于共同的sqiecesping.见表3TheelectronicspectraldataalongwithligandfieldparametersarepresentedinTable3.Theelectronicspectraof[Cr(L1)2(H2O)2]Cland[Cr(L2)2(H2O)2]Clshowbandsintherangeof17982～18210cm-1,23940～24440and35981～35679cm-1,whichmaybeassignedto4A2g→4T2g(F)(ν1),4A2g→4T1g(F)(ν2)and4A2g→4T1g(P)(ν3)transitions,respectively.Thevaluesofmagneticmomentforthesecomplexesare3.92and3.88B.M.,respectively.Thustheoctahedralgeometryhasbeensuggestedforthesecomplexes.Theelectronicspectraof[Co(L1)2(H2O)2]and[Co(L2)2(H2O)2]exhibitthreebandsintheregionof9631～9281cm-1,14751～15540cm-1and20025～20480cm-1whichhavetentativelybeenassignedto4T1g→4T2g(F)(ν1),4T1g→4A2g(F)(ν2)and4T1g→4T1g(P)(ν3)transitions,respectively.Themagneticmomentvaluesofthecomplexesare5.06and4.98B.M.Theobservedtransitionsareconsistentwithanoctahedralgeometry.Theelectronicspectraofthe[Ni(L1)2]3H2Oand[Ni(L2)2]2H2Oshowtwobandsat13811～13212cm-1and19351～18620cm-1assignableto1A1g→1Eg(1)and1A1g→1B2gtransitions,respectively.Thesearediamagneticcomplexes;thereforesquareplanargeometryhasbeensuggestedfortheseNi髤complex.TheelectronicspectraoftheCu髤complexofL1Hshowtwobandsat14212cm-1and19518cm-1assignableto2B1g→2B2gand2B1g→2Egtransitionsrespectively.Sincethevalueofmagneticmomentis1.97B.M.thereforesquareplanargeometryhasbeensuggestedforCu髤complex.TheelectronicspectrumoftheCu髤complexofL2Hdisplaysasinglebroadbandat14480cm-1correspondingtotransition2Eg→2T2g.Thevalueofmagneticmomentforthiscomplexis1.82B.M.;thustheoctahedralgeometryhasbeensuggestedforCu髤complex.TheparameterslikeB(Racahparameters),Dq,covalencyfactorβandLFSEhavebeencalculatedforthecomplexes.2.5correspondingg和gn.spicassofnatindickingg标准TheESRspectraofCu髤provideinformationabouttheextentofthedelocalizationofunpairedelectron.ESRspectraofbothCu髤complexeshavebeenrecordedonX-bandandtheirg∥,g⊥,Δg,gavandGhavebeencalculated.ThevaluesofESRparametersg∥,g⊥,gav,ΔgandGforCu髤complexofL1Hare2.1992,2.1307,2.1535,0.0685and1.5322,respectively.Similarly,thecorrespondingvaluesforCu髤complexofL2Hare2.2375,2.0665,2.1235,0.1710and3.6512,respectively.ESRspectraofthecomplexesrevealtwogvalues(gandg).Sincetheg∥andg⊥valuesarecloserto2,g∥>g⊥suggestsatetragonaldistortionaroundtheCu髤ion.Thetrendg∥>g⊥>ge(2.0023)showsthattheunpairedelectronislocalizedindX2-Y2orbitalinthegroundstateofCu髤andspectraarecharacteristicofaxialsymmetry.Theg∥>2.3ischaracteristicofanionicenvironmentandg∥<2.3indicatesacovalentenvironmentinmetalligandbonding.Thegvaluesforthecomplexesarelessthan2.3,suggestingthecovalentenvironment.TheexchangecouplinginteractionbetweentwoCu髤ionsisexplainedbyHathawayexpressionG=(g∥-2.0023)/(g⊥-2.0023).AccordingtoHathaway,ifthevalueGisgreaterthanfour(G>4.0),theexchangeinteractionisnegligible;whereaswhenthevalueofGislessthanfour(G<4.0)aconsiderableexchangecouplingispresentinsolidcomplex.TheGvaluesfortheCu髤complexesarelessthanfourindicatingconsiderableexchangeinteractioninthecomplexes.2.6作为非参数检索剂的whichpondeThethermalbehaviorofmetalcomplexesshowsthatthehydratedcomplexeslosemoleculesofhydrationfirst;followedbydecompositionofligandmoleculesinthesubsequentsteps.ThethermaldegradationbehavioroftheNi髤complexofL1Hhasbeenstudiedbythermogravimetricanalysis.Thecomplexdecomposesinthreestepswithinthetemperaturerangeof30～750℃.TheTGcurveofthecomplexshowsthatinfirststepthecomplexstartsdecompositionat65℃.Eliminationoflatticewatermoleculeshasbeenobservedonincreasingthetemperatureupto120℃(remainingwt%,obs./cald.,93.12/92.04).Thecomplexdoesnotshowanyweightlossbetween120～210℃.After210℃insecondstep,aweightlosshasbeenobservedingeneralupto370℃correspondingtothelossofnoncoordinatedligandpartfromthecomplex(remainingwt%,obs./cald.,62.12/59.32),whichisconsideredtobetheremovalofthiazolemoiety.Above450℃inthirdstep,aninflectionoccursinthecurveandlossinweightgoesupto655℃.Thisindicatestheeliminationofcoordinatedpartofthecomplexes.After655℃,aplateauhasbeenobservedwhichcorrespondstometaloxideasanultimatepyrolysisproduct(remainingwt%,obs./cald.,23.42/19.54).TheDTGcurveofthecomplexshowspeakat102,325and610℃.ThethermaldegradationbehavioroftheCo髤complexofL2Hhasbeenstudiedbythermogravimetricanalysis.Thecomplexdecomposedinthreesteps.ThethermogramoftheCu髤complexofL2Hindicatesthatthecomplexisstableupto110℃.Above110℃infirststep,aneliminationoftwocoordinatedwatermoleculeshasbeenobservedbetweenthetemperaturerangeof110～205℃(remainingwt%,obs./calcd.,93.65/93.60).Abovethistemperatureinsecondstepaweightlosshasbeenobservedingeneralupto410℃indicatingthedecompositionoftheligandmoiety(remainingwt%,obs./calcd.,50.25/45.87),whichisconsideredtobetheremovalofbenzaldehydemoiety.Thedecompositionofremainingligandmoietyinthirdstepoccursbetween460～630℃,above620℃ahorizontalcurvehasbeenobtainedsuggestingtheultimatepyrolysisproductasmetaloxide(remainingwt%,obs./calcd.,24.70/20.52).DTGcurveoftheCu髤complexshowspeakat179,378and598℃.Apartfromevaluatingthethermalstabilityofthemetalcomplexes,thisstudyalsohelpstocharacterizethemetalcomplexes.2.7piloyn-循环境线上的activation.whichincivation,etThekineticevaluationsofthethermaldecompositionofthecomplexeswerecarriedout.Allstageswereselectedforthestudyofkineticsofdecompositionofcomplexes.ThekineticparametersdataaresummarizedinTable4.Onthebasisothermaldecomposition,thekineticanalysisparametersuchasactivationenergy(E*),pre-exponentialfactor(Z),entropyofactivation(ΔS*),enthalpyofactivation(ΔH*)andfreeenergyofactivation(ΔG*)werecalculatedbyusingPiloyan-NovikovaandCoatsRedfernequation.Piloyan-Novikova:ln[α/T2]=ln[ZR/(βE*)]-E*/(RT)Coats-Redfern:ln[g(α)/T2]=ln[ZR/(βE*)]-E*/(RT)whereαisthefractionofthereactedmaterial,Tistheabsolutetemperature,g(α)isintegralmechan-ismfunction,E*istheactivationenergyinkJ·mol-1,Zisthepre-exponentialfactor,βistheheatingrateandRisthegasconstant.Astraightlineplotofthelefthandsideoftheaboveequationsagainst1/TgivesthevalueofE*andZfromtheslopeandtheinterceptrespectively.Theentropyofactivation(ΔS*),enthalpyofactivation(ΔH*)andfreeenergyofactivation(ΔG*werecalculatedusingthefollowingequation:ΔS*=2.303(logZh/kT)RΔH*=E*-RTΔG*=ΔH*-TΔS*wherekandharetheBoltzmannandPlanckconstant,respectively.Thehighvaluesofactivationenergiesreflectthethermalstabilityofthecomplexes.Thecomplexeshavenegativeentropy,whichindicatesthatthedecompositionreactionsproceedwithalowerratethanthenormalones.Thenegativevalueofentropyalsoindicatesthattheactivatedcomplexeshaveamoreorderedandmorerigidstructurethanthereactantsorintermediates.Thenegativevaluesoftheentropiesofactivationarecompensatedbythevaluesofenthalpiesofactivation,leadingtoalmostthesamevaluesforthefreeenergyofactivation.2.8日起算法重要目标函数营造了“phogge”循环在全球最短的分类第5................4和......和.和..................................X-raydiffractionwasperformedofmetacomplexes.TheXRDpatternsindicatecrystallinenatureforthecomplexes.X-raypowderdiffractogramofthecomplexeswererecordedusingCuKαassourceintherange5°～70°(2θ).X-raycrystalsystemhasbeenworkedoutbytrialanderrormethodsforfindingthebestfitbetweenobservedandcalculatedsin2θ.ThediffractogramofNi髤complexofL1Hhasrecorded12reflectionswithmaximaat2θ=7.97465withinterplanardistanced=11.07775nm.Thecomplexcrystallizedintetragonalsystem.Sin2θandhklvaluesfordifferentlatticeplaneshavebeencalculated.Crystaldataforcomplex,a=b=1.5671nm,c=2.3244nm,V=570.798nm3,Z=6,Dobs=1.3386g·cm-3andDcal=1.2864g·cm-3.Theobservedandcalculatedvaluesofdensityandsin2θshowgoodagreement.2.9temper对elicacivation和两物系统集体的重新定义elopererrohening.u.案例见表3Thetemperaturedependenceofthesolidstateconductivity(σ)ofthecompoundsintheircompressedpelletformhavebeenmeasuredatfixedfrequency1KHzinthetemperaturerangeof297～413K.ThevaluesofthesolidstateelectricalconductivityoftheSchiffbase,itscomplexesincreasewithincreasingtemperature,decreaseuponcoolingoverthestudiestemperaturerangeindicatingtheirsemiconductingbehavior.ThegeneralbehaviorofelectricalconductivityfollowstheArreheniusequation:σ=σoexp[-Ea/(KT)]whereEaisthethermalactivationenergyofconduction,σoistheconductivityconstant,kistheBoltzmanconstant.Thelotsofσvs1000/Tforallthecompoundsarefoundtobelinearoverastudiestemperaturerange.Theroomtemperatureelectricaconductivityofallthecompoundsliesintherangeo1.21×10-6～5.42×10-9Ω·cm-1.Thesevaluesshowtheirsemi-conductingnature.TheelectricalconductivityaroomtemperatureforthecomplexesofL1HareCr>Co>Cu>NiandforthemetalcomplexesofL2HisCo>Cr>Cu>Ni.Theactivationenergyofthecompoundliesintherange0.248～0.785eV.Theconfirmingothetemperaturedependenceconductivityofthecompoundswasalsocheckedbytherepeatingoftheconductivitymeasurements.2.10bactericica必要关于是否劳动价值钢的反应Thein-vitroAntimicrobialactivityofthesynthesizedSchiffbaseligandsandtheircorrespondingmetalcomplexesonselectedbacteriaEcoliandS.a