阴离子型菱形网状的手性多孔铟金属有机框架合成结构和氮气吸附Word下载.docx
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阴离子型菱形网状的手性多孔铟金属有机框架合成结构和氮气吸附Word下载.docx
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synthesis,structureandnitrogengasadsorption?
LipingWang,TianyouSong,LiangliangHuang,JianingXu,*ChaoLi,CaixiaJi,LiangShan
a
andLiWang*
Received21stJanuary2011,Accepted18thMarch2011
DOI:
10.1039/c1ce05110e
aaabaaa
AnovelporouschiralIn-MOFInH(D-C10H14O4)2
(1)withaleft-handedhelicalchannelassembledfromD-(+)-camphoricacid(D-H2Cam),hasbeenpreparedundersolvothermalconditions.Single-crystalX-raydiffractionanalysisrevealsthatcompound1crystallizesinthetetragonalspacegroup
3
Z?
4.Theframeworkfeatureofcompound1ischaracteristicoffour-connectedanionic-typediamondnetwithleft-handedchiralchannel.Moreover,compound1exhibitshighsurfacearea.
P43212(no.96)withparameters:
a?
13.8954A,b?
13.8954A,c?
17.7870A,V?
3434.4(7)A
Introduction
Thedesignandsynthesisofporousmetal–organicframeworks(MOFs)withcharacteristicstructuralchiralityaretopicsofcurrent
1,2
interestandofgreatchallengeinmaterialsscience,notonlyduetotheirintriguingstructures,butalsoowingtotheirpotentialapplicationsasfunctionalmaterialsforenantioselectivecatalysis
3–7
andseparation,non-linearoptics,ferroelectricsandmagnetism.Recently,thesynthesisofchirallow-connectivity(3-or4-connected)MOFsattractsspecialattentiononaccountsoftheir
8
appealingarchitecturesandhighsurfaceareas.Toourknowledge,comparedwithtremendoussuccessinthesynthesisoflow-connectivityframeworkmaterialsinthepastdecades,3Dchirallow-connectivityMOFsarestillrare.
DoPwubnllisoahededdonby13NAAprNilJI20N11Gon
pseudotetrahedralgeometrywhichcanbeconsideredasa4-connectednode.
WeareinterestedinthedesignandsynthesisofporouschiralMOFs,especially,chirallow-connectivityIn-MOFs.Thelitera-turestudiesindicatedthatoneofthemosteffectiveanddirectapproachestopreparechiralMOFsistouseenantiopurechiralligandsasstartingmaterialswhichimparthomochiralitytothe
11
resultingcrystals.Todate,thesynthesisofchiralMOFshasachievedhugesuccessthroughnaturallyorganicligandswithchiral
12
polycarboxylategroupsandpolypyridylgroups.Amongthem,D-camphoricacid(D-H2Cam),asanenantiopureditopicorganiclinker,hasconstructedavarietyofchiralMOFsoftransitionmetals,suchas[M2(D-Cam)2(4,4-bpy)]n(M?
Cu,Zn)containingahomochiralgrid-like(4,4)layeredstructure,Co(D-Cam)1/2(bdc)1/2(tmdpy)exhibitinghomochiraltopologyofquartzdualnetandNi(D-cam)(H2O)2withhomochiralsrstopology.ThuswechooseD-H2Camasorganicligandtosynthesizethenewchirallow-connectivityIn-MOF.Finally,anovelanion-typediamondnetworkInH(D-C10H14O4)2
(1)withaleft-handedchannelwasobtainedundersolvothermalcondi-tions.ItisnotedthattheanionicframeworkspracticallythatofchiralanionicMOFs,arestillrarelyoccurredinMOFs,eventhisphenomenonisverycommoninzeolites,phosphatesandotheroxides.Herein,wedescribethesynthesis,crystalstructureandcharacterizationofcompound1,alongwithnitrogengasabsorptionproperty.
13
Morerecently,In-MOFscontinuetoreceivemuchattentionduetotheirflexiblecoordinationcharacteristics(six,sevenandeight)andexceptionalgasabsorptionandcatalyticpropertyusedas
8c,9
heterogeneousLewisacidcatalystsinorganictrans-formations.Furthermore,In-MOFscanbeamoreattractivechoiceinthedesignoflow-connectivityandhighsurfaceareaMOFsbecauseofitseight-coordinatecentralbuildingblockwithfourequivalent
10
carboxylateligands.Forexample,inquartz-likechiralInH(BDC)2,theindiumcentersadopttriangulateddodecahedralgeometriesbythechelationoffourcarboxylategroupsfromfourterephthalateanionstoformahighlydistorted
CollegeofChemistry,JilinUniversity,Changchun130012,Jilin,P.R.China.E-mail:
lwang99@;
Fax:
+86-431-85671974;
Tel:
+86-431-85168471
b
StateKeyLaboratoryofInorganicSynthesis&
amp;
PreparativeChemistry,CollegeofChemistry,JilinUniversity,Changchun130012,Jilin,P.R.China.E-mail:
xujn@;
+86-431-
Experimental
Materialsandmeasurements
85168471?
Electronicsupplementaryinformation(ESI)available:
Detailsofthestructureinformation,PXRD,IRandTGAofcompound1.CCDCreferencenumber808780.ForESIandcrystallographicdatainCIForAllchemicalswereobtainedfromcommercialsourcesandusedwithoutfurtherpurification.PowderX-raydiffraction(PXRD)datawereobtainedusingSHIMADAZUXRD-6000diffrac-
tometerwithCu-Karadiation(l?
1.5418A),withthestepsize
CrystEngComm,2011,13,4005–4009|4005otherelectronicformatseeDOI:
10.1039/c1ce05110eThisjournalisaTheRoyalSocietyofChemistry2011
10.1039/C1C01EJu05ly1120011EDowPnluboalisdeheddbyonN13AANprJIilN20G11UonNhtItpV:
//EpuRbsSI.rsTc.Yorong|
andthecounttimeof0.02and4s,respectively.Theelemental
analysiswasconductedonaPerkinElmer2400elemental
analyzer.ICP-AES(inductivelycoupledplasma-atomicemissionspectroscope)analysiswasperformedonaPerkinElmerOptima3300DVICPinstrument.FT–IRspectrumwasrecordedon
1
aNicoletImpact410spectrometerbetween4000and400cm
Spacegroup
a/A
usingtheKBrpelletmethod.Thermogravimetricanalysis(TGA)
wasconductedonaPerkin-ElmerTGA7thermogravimetric
b/A
c/A
analyzerwithaheatingrateof10Cminfromroomtemper-atureto800C.GassorptionexperimentwascarriedoutwithaMicrometricsASAP2020instrument.
R(F)Nets
Flacka
P4321213.8954(15)13.8954(15)17.787
(2)0.0658
0.16(10)
P4321213.7393
(1)13.7393
(1)37.2281(5)0.0798
Dia
Ths
0.03(7)
P43212
13.7548
(2)13.7548
(2)38.1612(8)
0.0767
0.02(8)
SynthesisofInH(D-C10H14O4)2
(1)
Allreagentswereofanalyticalgrade.Compound1was
solvothermallypreparedfromastartingmixturecontainingindiumtrichloride(InCl3),D-(+)-camphoricacid(D-H2Cam),
ethylenediamineanhydrous(EDA)andN,N-dimethylforma-mide(DMF).IndiumtrichloridewasobtainedhydrothermallybydirectreactionofIn2O3withHClat180Cfor2dunderautogenouspressure.ThemolarratiooftheinitialmixturewasInCl3:
D-H2Cam:
EDA:
DMF?
1:
2:
6:
362.Themixturewasfurtherstirredforonehouratroomtemperatureandheatedat100Cfor3dina23mLTeflon-linedstainlesssteelautoclave(filledupto30%volumecapacity),thenslowlycooleddowntotheambienttemperature.Colourlessblockcrystalsofcompound1werecollectedbyfiltration,washedwithDMFandair-dried.Theyieldofproductwas57%inweightbasedonindium.Inordertocheckthephasepurityoftheproducts,powderX-raydiffraction(PXRD)experimentshavebeencarriedoutforthecompound1(Fig.S1?
).TheagreementbetweentheexperimentalandsimulatedpowderX-raydiffractionpatternsindicatedthephasepurityoftheas-synthesizedproduct.Thedifferencesinintensitymaybeowingtothepreferredorientationofthepowdersamples.TheICPandelementalanalysis:
found(wt%)In17.05,C46.25,H6.23,N4.00;
calcd(wt%)In16.97;
C46.13,H6.65,N4.14.IRspectrum(KBr/cm):
3452(br),2966(w),2455(br),2067(w),1639(s),1564(vs),1415(s),1130(vs),848(m),541(m).
?
D-camphoricacid,EMIm?
1-ethyl-3-methylimidazolium,
BMIm?
1-butyl-3-metylimidazolium.Dia?
diamond,Ths?
ThSi2topology.
D-H2cam
Table1,whiletheselectedbondlengthsandanglesarepresented
inTableS1?
.
Gassorptionmeasurement
Beforethemeasurement,thesampleof1wassoakedinmethanol
for3dtoremoveDMFandH2Osolventmolecules,then
filtrated,anddriedatroomtemperature.Then,thesamplewas
5
pretreatedunderhighvacuum(lessthan10Torr)at80Covernighttoremovemethanolandallresiduesolventsinthechannels.About100mgofthedesolvatedsamplewasusedfor
theentireadsorptionmeasurement.
Resultsanddiscussion
Structuraldescription
that1Flack
Asingle-crystalX-raydiffractionanalysisindicatescrystallizesinachiralP43212spacegroup,withthe
parameterof0.16(10).AsshowninFig.1,theasymmetricunitofthecompound1containsonecrystallographicallyindepen-dentIn(III)ion.EachIn(III)ioniseightcoordinatedbyeightcarboxylateoxygenatomsfromfourD-Camligandstoform
adodecahedralmotif,whichexhibitshighcoordinatingabilityofmaingroupelements.In–OdistancesandO–In–Obondanglesarerangingfrom2.219(9)to2.392(8)Aand56.1(3)to164.1(3),
respectively,whichare
always
observedforother
Single-crystalX-raycrystallography
Asuitablesinglecrystalofcompound1(0.10.10.1mm)wasselectedforsingle-crystalX-raydiffractionanalysis.TheintensitydatawerecollectedonaSiemensSmartCCDdiffrac-
In(III)-
carboxylateframeworks.Thetwocarboxylateoxygenatomsof
16
tometerwithgraphite-monochromatedMo-Ka(l?
0.71073A)radiationatatemperatureof293
(2)K.Nosignificantdecaywasobservedduringthedatacollection.DataprocessingwasaccomplishedwiththeRAPIDAUTOprocessingprogram.Thestructurewassolvedbydirectmethodandrefinedbyfull-matrix
2
least-squaresonFusingtheSHELXTLcrystallographicsoft-
14,15
warepackage.Alltheindiumatomswerelocatedfirst,andthentheoxygenandcarbonatomsweresubsequentlyfoundindifferenceFourier
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- 关 键 词:
- 阴离子 菱形 网状 手性 多孔 金属 有机 框架 合成 结构 氮气 吸附