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
进),
;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:1002—0721(2003)01一OO09—04
;Anumberoflanthanideternarycomplexescon-
;tainingheterocyclicamineshavebeenreportedsince
;1960[.Inrecentyearsmuchattentionhasbeenpaid
;toquaternarycomplexesoflanthanidesbecauseofin-
;terestingstructure,coordinationmode,competitionre-
;actionandproperty[圳.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 ;recordedintherangeof4000，4OOem，onaShi.
;madzu470IRspectrophotometerinKBrpellet.UV. ;visiblespectrumwasrecordedonaBeckmanDU.50 ;spectrophotometerinethano1.DTA.TGspectrumwas ;carriedoutinaironaRigaku8150DTA.TGthermom. ;eterwiththeheatingrate10??min，.ESRspectra
;wererecordedonaJES.FEIXGspectrometeroperated ;inX-bandatfieldmodulationfrequency100kHz.mi- ;crowavepower4mW,responsetime0.3s,field ;sweeprange0，0.6Tandmicrowavefrequency
;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:2001—07—12;rcgl~date:2002—01—30
;Foundationitem:ProjectsupportedbytheNationalNaturalScienceFoundationofChina(50073019)
;Biography:ZhuLongguan(1964
一),Doctor,Professor;Researchinterest:Functionalcoordinationchemistry
;*Comspun~tnSauthor(E—mail:chezlg@zju.edu.cn.)
;
;10
;andDMF.Atroomtemperaturethemolarconductance ;inDMSO(1×10mol?L)is76S?cm?mol，,
;whichsuggestsnon-electrolytecomplexaccordingto
;theRef.[12].
;2lsuitsandDiscussion
;2.1Characterizationofthecomplex
;ThereisnoabsorptionoffreeNO一(，1390
;cm)observed,whichisconsistentwiththeelectric ;conductivityvalue.BI(P4),Al(I),A2(2)andB2 ;(6)absorptionpeaksofthecoordinatedNO3一are
;1512.1288.1026and780cminthecomplex,re. ;spectively.Av=Bl(p4)一Al(1)=224cm，,which
;suggeststhatNO3一isbidentatetotheGd?.The
;strongC—Houtplanevibrationabsorptionsinthe ;spectrumoffreephen,appearingat739and856 ;cm，.areshiftedto730and850cm，whenphenco.
;ordinates.Thepeakof(coo)isat1428cmwhile ;the(CO0)isat1595cm一.Av=(CO0)一
;(CO0)<200cm，,whichindicatesthatpropionates ;bridgeGd(mionsaccordingtotheDeaconrule. ;Fromaboveinformationthecomplexcanbesuggested ;thatitisbinuclearormultinuclear.
;TheUVabsorptionsofphenareat227.5and ;261.5aminethanolatroomtemperature.whilethey ;areshifted1.5nininthecomplex.whichshowsthat ;Gd?haslittleeffectontheringconjugationof1.10一
;phenanthroline.I1lisphenomenonisverypopularin ;thelanthanideternarycomplexescontaining ;phen[14，..
;DTA.TGcurveshowsthatphenandonepropi. ;onatewaslostsimahaneouslyat320—.385oCwith
;weightlossof48.7%.TheresidueofGd2Owasob. ;tainedat800?.
;ESRspec~aofpolycrystallinepowderandits ;DMSOsolutionwererecoredat298oC.Ingenera1. ;Gd”ionexhibitsUspectrumcharacterizedbythree
;prominentfeatureswitheffectivegvaluesof，6.0.
;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仃(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，,
;肚(MoKa)=33.63mm，,F(000)=530andGOF=
;1.80.
;Theatomiccoordinateandthermalparametersare ;listedinTable1.andtheselectedbondlengthsand ;anglesareveninTable2.TheatomsC(17)andC ;(18)aredisorder.Themolecularstructureisshownin ;Fig.2.I1lestackingviewofthecomplexincrystalis ;showninFig.3.Thedistancebetween1【一1【stacked
;phenanthrolineligandsfromneighboringmoleculesis ;about0.36am.ThecomplexisadimerwithaGd.Gd ;separationof0.3878nmandpossessesacenterof ;symmetry.Eachgadoliniumatomisnine.coordinated ;withamonocappedsquareantiprismgeometryandin—
;volvesfiveoxygenatomsfromfourpropionates,two ;nitrogenatomsfromphenandanothertwooxygenat-
;omsfromanitrategroup.ThefourCHCH2CO0一an.
;iOIlSinthedimercomplexshowtwocoordination ;modes.whichisverydi佑culttodistinguishthemfrom ;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)一Gd(1)and0(6)一Gd(1),respectively.
;Distancesofca(1)一O(NO3)arelongerthanthatof
;Gd(1)一O(CO0)exceptGd(1)一0(6),attributed
;tostrongbondingofpropionateswithmetalion. ;Phenanthrolineligandsaresituatedinthevacant ;sides,andthereforethecomplexhaslittlestericexclu—
;sion.
;Table2,Selectedb0ndle(nln)andangles(.) ;N(3)一0(1)andN(3)一0(2)bondlengths
;fromthenitrateanionsare0.1252and0.1272nm. ;respectively.AccordingtoPaulingStheory引.the
;bondordersofN(3)一O(1)andN(3)一0(2)axe1.66
;and1.56,respectively,whicharevaluesbetweensin. ;gleanddoublebonds.ButthebondorderofN(3)一0
;(3)is1.90,andclearlyitisadoublebond. ;Table1Fractionalatomiccoordinatesandthermalpro’ran?
;eters(m2)fornon-hydrogenaW
;syIllill~code:一,一Y.一
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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
—
;contentandthedefectoftheneedleholesinA1一
SialloygencontentinlanthanumisthemainreasonOfincreasing ;wereanalyzedbyDeglemethodandthedecompressionhydrogencontentinA1一
alloy,andatthesametime,
;sohdificationmethod.eresultsindicatethatthecont.1evelofhydrogencontentinlanthanumanditseffect
son
;entofthehydrogenandthedefectoftheneedleholesinthehydrogencontentintheL1.Sialloywagdiscuss
ed.
;thealuminumalloyapparentlyincreaseafteradditionOf ;Keywords:rareearths;lanthaIlu『n:AI—alloymelts;hydrogen
;(SeeJ.Chin.RE.Soc.(inChin.),20O3,21(1):49forfulltext) ;
;