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.docx
《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.docx》由会员分享，可在线阅读，更多相关《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.docx（12页珍藏版）》请在冰豆网上搜索。
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
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
doi:
10.1039/C1C01EJu05ly1120011EUNIhttVEp:
//RSpubITs.rsYoc.onrg|
ViewOnline
CrystEngComm
DynamicArticleLinks
C
Citethis:
CrystEngComm,2011,13,4005
www.rsc.org/crystengcomm
PAPER
AporouschiralIn-MOFwithanionic-typediamondnetwork:
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
a
CollegeofChemistry,JilinUniversity,Changchun130012,Jilin,P.R.China.E-mail:
lwang99@;Fax:
+86-431-85671974;Tel:
+86-431-85168471
b
StateKeyLaboratoryofInorganicSynthesis&PreparativeChemistry,CollegeofChemistry,JilinUniversity,Changchun130012,Jilin,P.R.China.E-mail:
xujn@;Fax:
+86-431-85671974;Tel:
+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
doi:
10.1039/C1C01EJu05ly1120011EDowPnluboalisdeheddbyonN13AANprJIilN20G11UonNhtItpV:
//EpuRbsSI.rsTc.Yorong|
ViewOnline
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.
1
R（F）Nets
Flacka
P4321213.8954（15）13.8954（15）17.787
（2）0.0658
b
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）
Ths
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,
b
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
1
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-
3
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
升级会员 