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Synthesis,

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Synthesis,is

    Synthesis,

JoURNALOFRAREEARTHs

    ;Vo1.21,No.1,Feb.2003,P.9

    ;Synthesis,CharacterizationandCrystalStructureofQuaternary

    ;ComplexofGadoliniBin(?)

    ;Zhul_~ngguan(朱龙观),CaiGuoqiang(蔡国强1,WangGuoping(王国平).,SusumuKitagawa(北川

    ),

    ;ShigeyukiMasaoka(正冈重行)

    ;(J.DepartmentofChemistry,ZhejiangUniversity,Hangzhou310027,China;2.DepartmentofSyntheticChem-

    ;istryandBiologicalChemistry,FacultyofEngineering,KyotoUniversity,Kyoto606-8501,Japan) ;Abstract:Anewquaternarymixedanioncomplexofgadolinium(m),[Gd(CH3cH2coo)2(NO3)(phen)]2,wassynthe-

    ;sizedandstructurallycharacterized.eESRspectrumofthecomplexwitheffectivevaluesof5.314,2.473and1.880

    ;inpolycrystallinepowderatroomtemperatureisquitedifferentfromtheUspectrum.ThecoordinationnumberofGd?is

    ;ninewithamonocappedsquareantiprismgeometry.Andthestackingeffectwasobservedinthecomplex.ecrystalof

    ;thecomplexbelongstotriclinicwithspacegroupPl,a:0.9626(4)am,b=0.9732(4)am,c:1.1758(5)am,ot=

    ;102.45(1).,=108.16(1).,y=96.68(2).,V=1.0018(7)am,Z=2,D=1.80g?cm,(MoKa)=33.63

    ;mill

    ;,F(O00)=530,GOF=1.80,R=0.023andR=0.027.

    ;Keywords:organicchemistry;gadolinium(?);crystalstructure;mixedligands;ESR;quaternarycomplex;rareearths

    ;CLCnumber:0614.33;0641.4Documentcode:AArticleID:10020721(2003)01OO0904

    ;Anumberoflanthanideternarycomplexescon-

    ;tainingheterocyclicamineshavebeenreportedsince

    ;1960[.Inrecentyearsmuchattentionhasbeenpaid

    ;toquaternarycomplexesoflanthanidesbecauseofin-

    ;terestingstructure,coordinationmode,competitionre-

    ;actionandproperty[.ESRcanexhibitthespin

    ;state,coordinationstructureanddifferentelectronen.

    ;ergylevelsoftheparamagneticionsL10.whichmakes

    ;usclearlyunderstandstructuralcharacteristicsofeom-

    ;plexes.Thereisonlyonereportforquaternaryeom-

    ;plexaboutESRproperty..Tostudyfurtherthequa-

    ;ternarycomplexes,weherereportsynthesis,eharac

    ;terizationandcrystalstructureof[Gd(CH3CH2CO0)2

;(NO)(phen)]2.

    ;1Experimental

    ;1.1Physicalmeasurementsandmaterials ;ElementalanalysiswascarriedoutusingCarlo ;Erba1106elementalanalyzer.Infraredspectrumwas ;recordedintherangeof40004OOemonaShi.

    ;madzu470IRspectrophotometerinKBrpellet.UV. ;visiblespectrumwasrecordedonaBeckmanDU.50 ;spectrophotometerinethano1.DTA.TGspectrumwas ;carriedoutinaironaRigaku8150DTA.TGthermom. ;eterwiththeheatingrate10??min.ESRspectra

    ;wererecordedonaJES.FEIXGspectrometeroperated ;inX-bandatfieldmodulationfrequency100kHz.mi- ;crowavepower4mW,responsetime0.3s,field ;sweeprange00.6Tandmicrowavefrequency

    ;9.445GHz.

    ;ThepurityofGd203(Fluka)exceeds99.9%.AU ;otherchemicalspurchasedfromseveralchemicalcom. ;panicsareofanalyticalreagentgradeandusedasre- ;ceived.

    ;1.2Preparationof[Gd(CH3CH2COO)2

    ;(NO3)(phen)]2

    ;Gd(NO3)3?nH20(0.2mmo1)preparedfrom

    ;Gd2O3andnitricacidwasdissolvedinamixtureof ;ethanol(5m1)andwater(2m1).Asolutionof1,10. ;phenanthroline(0.63mmo1),8-hydroxyquinoline ;(HQ,1.0mmo1)andCH3CH2COOH(50%,3m1)

    ;inethanol(10mUwasaddedtotheabovesolution. ;Afteraboutoneweek,crystalswereobtained.Ana1. ;Caled.(%)for[Gd(CH3CH2coo)2(NO3)(phen)]2: ;C,39.63;H,3.33;N,7.70;Gd,28.82.Found ;(%):C,39.59;H,3.31;N,7.85;Gd,28.92. ;Thesolubilityofthecompoundispoorinnon——polar

    ;solventsandthecompoundslightlydissolvesinDMSO ;Receiveddate:20010712;rcgl~date:20020130

    ;Foundationitem:ProjectsupportedbytheNationalNaturalScienceFoundationofChina(50073019)

    ;Biography:ZhuLongguan(1964

    ),Doctor,Professor;Researchinterest:Functionalcoordinationchemistry

    ;*Comspun~tnSauthor(Email:chezlg@zju.edu.cn.)

    ;

    ;10

    ;andDMF.Atroomtemperaturethemolarconductance ;inDMSO(1×10mol?L)is76S?cm?mol,

    ;whichsuggestsnon-electrolytecomplexaccordingto

;theRef.[12].

    ;2lsuitsandDiscussion

    ;2.1Characterizationofthecomplex

    ;ThereisnoabsorptionoffreeNO(1390

    ;cm)observed,whichisconsistentwiththeelectric ;conductivityvalue.BI(P4),Al(I),A2(2)andB2 ;(6)absorptionpeaksofthecoordinatedNO3are

    ;1512.1288.1026and780cminthecomplex,re. ;spectively.Av=Bl(p4)Al(1)=224cm,which

    ;suggeststhatNO3isbidentatetotheGd?.The

    ;strongCHoutplanevibrationabsorptionsinthe ;spectrumoffreephen,appearingat739and856 ;cm.areshiftedto730and850cmwhenphenco.

    ;ordinates.Thepeakof(coo)isat1428cmwhile ;the(CO0)isat1595cm.Av=(CO0)

    ;(CO0)<200cm,whichindicatesthatpropionates ;bridgeGd(mionsaccordingtotheDeaconrule. ;Fromaboveinformationthecomplexcanbesuggested ;thatitisbinuclearormultinuclear.

    ;TheUVabsorptionsofphenareat227.5and ;261.5aminethanolatroomtemperature.whilethey ;areshifted1.5nininthecomplex.whichshowsthat ;Gd?haslittleeffectontheringconjugationof1.10

    ;phenanthroline.I1lisphenomenonisverypopularin ;thelanthanideternarycomplexescontaining ;phen[14..

    ;DTA.TGcurveshowsthatphenandonepropi. ;onatewaslostsimahaneouslyat320.385oCwith

    ;weightlossof48.7%.TheresidueofGd2Owasob. ;tainedat800?.

    ;ESRspec~aofpolycrystallinepowderandits ;DMSOsolutionwererecoredat298oC.Ingenera1. ;Gd”ionexhibitsUspectrumcharacterizedbythree

    ;prominentfeatureswitheffectivegvaluesof6.0.

    ;2.8.and2.0superimposedonabroadresonanceline ;shape.ButtheESRspectrumofthesolidcomplexis ;quitedifferentfromtheUspectrumwitheffectiveg ;valuesof5.314,2.473and1.880(seeFig.1).Sim

    ;ilarphenomenonalsowasobservedinotherquaternary ;complexes”J.InDMSOsolutionthecomplexexhibits

    ;singlepeak,g=1.949,whichisduetothedynamic ;disordered’effectcausedbymolecularthermalmotion.

    ;AndthelinewidthofthecomplexinDMSOissmaller ;thanthatofthepowder.

;2.2Crystalstructure

    ;Acolorlessneedlecrystalhavingapproximatedi- ;JoURNALOFRAREEARTHS.Vo1.21.No.1,Feb.2003 ;Fig.1PolycrystallinepowderESRspectrumofthecomplexat ;roomtemperature

    ;mensionsof0.5mm×0.35mm×0.20mmwas

    ;mountedonaglassfiber.Thedatawerecollectedat ;roomtemperatureonaRigakuMercuryCCDdiffrac- ;tometerwithgraphitemonochromatedMoKa(= ;0.071069Bin)radiationtoamaximum20valueof ;54.2..Total6543reflectionswerecollectedand3989 ;wereunique(R_nl=0.013).Thedatawerecorrected ;forLorentzandpolarizationeffects.111estructurewas ;solvedbydirectmethodsandexpandedusingFourier ;techniques.Thenon.hydrogenatomswererefined ;anisotropically.Hydrogenatomswereincludedbutnot ;refined.ThefinalcycleoffuII.matrixleast.squaresre. ;finementWasbasedon3778observedreflections(I> ;3.0(I))and280variableparametersandconverged ;withunweightedandweightedagreementfactorsofR ;=

    ;0.023andR=0.027.AIIcomputationswerecar. ;riedona0S2WorkstationusingteXsansoftware. ;DrawingswereproducedwithORTEP-3program. ;Crystaldataforthecomplexareasfollows:thecrystal ;istriclinic,spacegroupP1,thu=0.9626(4) ;nnl,b=0.9732(4)nm,c=1.1758(5)nm,ot=

    ;102.45(1).,=108.16(1).,y=96.68(2).,V= ;1.0o18(7)nm,Z=2,D=1.80g?cm,

    ;(MoKa)=33.63mm,F(000)=530andGOF=

    ;1.80.

    ;Theatomiccoordinateandthermalparametersare ;listedinTable1.andtheselectedbondlengthsand ;anglesareveninTable2.TheatomsC(17)andC ;(18)aredisorder.Themolecularstructureisshownin ;Fig.2.I1lestackingviewofthecomplexincrystalis ;showninFig.3.Thedistancebetween1【一1stacked

    ;phenanthrolineligandsfromneighboringmoleculesis ;about0.36am.ThecomplexisadimerwithaGd.Gd ;separationof0.3878nmandpossessesacenterof ;symmetry.Eachgadoliniumatomisnine.coordinated ;withamonocappedsquareantiprismgeometryandin

    ;volvesfiveoxygenatomsfromfourpropionates,two ;nitrogenatomsfromphenandanothertwooxygenat-

;omsfromanitrategroup.ThefourCHCH2CO0an.

    ;iOIlSinthedimercomplexshowtwocoordination ;modes.whichisverydiculttodistinguishthemfrom ;IRspectrum:onemodebondstotwogadoliniumatom ;throughO(4)andO(7);theothermodeischelatedto ;

    ;ZhuLGeta1.Synthesis,CharacterizationandCrystalStructureofQuaternaryComplexofGd(?)ll ;C(15)

    ;Fig.2Molecularstructureofthecomplex ;5

    ;(6)

    ;Fig.3Stackingviewofthecomplexamongmolecules(only ;oneoxygeniskeptexceptphenforclarity) ;onegadoliniumatomthroughO(5)andO(6)andsi

    ;muhaneouslyoxygen0(6)bindsanothergadolinium ;atomwithdistancesof0.2341nmand0.2529nmfor ;O(6)Gd(1)and0(6)Gd(1),respectively.

    ;Distancesofca(1)O(NO3)arelongerthanthatof

    ;Gd(1)O(CO0)exceptGd(1)0(6),attributed

    ;tostrongbondingofpropionateswithmetalion. ;Phenanthrolineligandsaresituatedinthevacant ;sides,andthereforethecomplexhaslittlestericexclu

    ;sion.

    ;Table2,Selectedb0ndle(nln)andangles(.) ;N(3)0(1)andN(3)0(2)bondlengths

    ;fromthenitrateanionsare0.1252and0.1272nm. ;respectively.AccordingtoPaulingStheory.the

    ;bondordersofN(3)O(1)andN(3)0(2)axe1.66

    ;and1.56,respectively,whicharevaluesbetweensin. ;gleanddoublebonds.ButthebondorderofN(3)0

    ;(3)is1.90,andclearlyitisadoublebond. ;Table1Fractionalatomiccoordinatesandthermalpro’ran?

    ;eters(m2)fornon-hydrogenaW

    ;syIllill~code:,Y.

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    ;********************

    ;ExperimentalAnalysisofHydrogenContentIncreaseinAI-AlloyMeltafterAddmg

    ;LaMetal

    ;YuYun”,JiChengchang,LiJianguo,ShangBaolu(1.SchoolofMaterialsScienceandEngineering. ;ShanghaiJiaotongUniversity,Shanghai200030,China;2.StateKeyLaboratoryofSolidificationPro

    ;cessing,NorthwesternPolytechnicalUniversity,’an710072,China)

    ;Abstract:TheeffectsOfrareearthLaonthehydrogenLamorethen0.3%.Itcanbededucedthatthehydro

    

    ;contentandthedefectoftheneedleholesinA1

    SialloygencontentinlanthanumisthemainreasonOfincreasing ;wereanalyzedbyDeglemethodandthedecompressionhydrogencontentinA1

    alloy,andatthesametime,

    ;sohdificationmethod.eresultsindicatethatthecont.1evelofhydrogencontentinlanthanumanditseffect

    son

    ;entofthehydrogenandthedefectoftheneedleholesinthehydrogencontentintheL1.Sialloywagdiscuss

    ed.

    ;thealuminumalloyapparentlyincreaseafteradditionOf ;Keywords:rareearths;lanthaIlun:AIalloymelts;hydrogen

    ;(SeeJ.Chin.RE.Soc.(inChin.),20O3,21(1):49forfulltext) ;

    ;

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