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Structure elucidation of a complex CO2-based organicframework material by NMR crystallography
Julien Leclaire, Guillaume Poisson, Fabio Ziarelli, Grard Ppe, FrdricFotiadu, Federico Paruzzo, Aaron J. Rossini, Jean-Nicolas Dumez, Bndicte
Elena-Herrmann, Lyndon Emsley
To cite this version:Julien Leclaire, Guillaume Poisson, Fabio Ziarelli, Grard Ppe, Frdric Fotiadu, etal.. Structure elucidation of a complex CO2-based organic framework material byNMR crystallography. Chemical Science, The Royal Society of Chemistry, 2016, 7 (7),pp.4379-4390. ..
https://hal.archives-ouvertes.fr/hal-01355480https://hal.archives-ouvertes.fr
DOI:10.1039/C5SC03810C(EdgeArticle)Chem.Sci.,2016,7,4379-4390Received7thOctober2015,Accepted22ndMarch2016Firstpublishedontheweb22ndMarch2016
Athree-dimensionalstructuralmodelofacomplexCO2-basedorganicframeworkmadefromhighmolecularweight,self-assembled,flexibleandmulti-functionaloligomericconstituentshasbeendetermineddenovobysolid-stateNMRincludingDNP-enhancedexperiments.Thecompleteassignmentofthe15N,13Cand1Hresonanceswasobtainedfromaseriesoftwo-dimensionalthroughspaceandthroughbondcorrelationexperiments.MM-QMcalculationswereusedtogeneratedifferentmodelstructuresforthematerialwhichwerethenevaluatedbycomparingmultipleexperimentalandcalculatedNMRparameters.BothNMRandpowderX-raydiffractionwereevaluatedastoolstodeterminethepackingbycrystalmodelling,andatthelevelofstructuralmodellingusedherePXRDwasfoundnottobeausefulcomplement.ThestructuredeterminedrevealsahighlyoptimisedH-bondingnetworkthatexplainstheunusualselectivityoftheself-assemblyprocesswhichgeneratesthematerial.TheNMRcrystallographyapproachusedhereshouldbeapplicableforthestructuredeterminationofothercomplexsolidmaterials. Structure elucidation of a complex CO2-based organic framework material by NMR crystallography Julien Leclaire,*ab Guillaume Poisson,ab Fabio Ziarelli,c Gerard Pepe,d Frdric Fotiadu,b Federico M. Paruzzo,f Aaron J. Rossini,ef Jean-Nicolas Dumez,e Bndicte Elena-Herrmann*e and Lyndon Emsleyf Corresponding authors a,Univ Lyon, Universit Claude Bernard, CNRS, INSA, CPE, ICBMS UMR 5246, 69622 Villeurbanne, France E-mail: julien.leclaire@univ-lyon1.fr b,Aix Marseille Universit, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France c,Aix-Marseille Universit, Fdration des Sciences Chimiques, Spectrople, 13397 Marseille, France d,Aix-Marseille Universit, CNRS, UMR 7325 CINaM, 13288 Marseille, France e,Universit de Lyon, Institut des Sciences Analytiques, Centre de RMN trs hauts champs, CNRS/ENS Lyon/UCBL, 69100 Villeurbanne, France E-mail: benedicte.elena@ens-lyon.fr f,Institut des Sciences et Ingnierie Chimiques, Ecole Polytechnique Fdrale de Lausanne (EPFL), 1015 Lausanne, Switzerland
http://dx.doi.org/10.1039/C5SC03810Chttp://dx.doi.org/10.1039/2041-6539/2010
Structure elucidation of a complex CO2-based organic framework material by NMR crystallographyIntroduction
Thelastdecadeshaveseenanexplosivegrowthintheproductionofrationallydesignedsupramolecularmaterialsresultingfromdirectedself-assemblyofmolecularbuildingunits.Amongtheseself-assembledmolecularnetworksdisplayingpromisingproperties,onecancitemetalorganicframeworks(MOFs),1obtainedbyconnectingmetalcontainingsecondaryunitswithorganiclinkers,andorganicsupramolecularsolids2resultingfromtheconnectionofcarbon-basedbuildingblocks.Theirsynthesisisbasedonattractiveone-potself-assemblyprocesseswhichillustratetheconceptofmoleculartectonics.35Self-organizationresultsfromthestructureofandtheinteractionsbetweentherigidbuildingblocks.6Short-range,stronganisotropicinteractionsdriveself-organizationacrosslengthscalesfromthemolecularandnano-scalelevel7uptothemicro-andmilli-scalelevels.811Thewell-definedbuildingunits,coupledwiththethermodynamiccontroloftheself-assemblyprocess,oftenleadtolongrangestructuralorderi.e.tohighlycrystallinesolids.12X-raydiffractioncanfrequentlybeusedtocharacterizethestructuralfeaturesoftheseself-assemblednetworksiftheyaresufficientlyregular.
Suchsupramolecularmaterialscanhavetunablephysicalandchemicalproperties,withcavitieswhosesizeandshapeareeasilymanipulated.13However,thecompletestructuralcharacterizationofincreasinglycomplexsystems,thatisessentialtodeterminestructureactivityrelationsandtothenrationallyimproveproperties,remainsaconsiderablechallenge.Thisnotablyoftenpreventsexplorationofmolecularassembliesbasedonmoreflexibleobjectsinvolvingmultiplefunctionalities.
Inthiscontextwehaverecentlysynthesizedanddescribedaself-assembledsupramolecularsolidwhichresultsfromtheone-potthermodynamicallycontrolledsimultaneousreactionoftwoorganicbuildingblocksandCO2(Scheme1).14Notably,thisreversibleCO2-basedorganicframeworkisproducedbyaggregationofflexibleself-complementaryoligomericobjects.AsillustratedinScheme1theseoligomericbuildingblocksarethemselvesassembledinsitufromthebasiccomponents,includingCO2.Thecovalentassemblyprocessoftheoligomersconsistsinthesimultaneousandreversibleformationof20carbonnitrogenbondsofthreedifferentchemicaltypes(imine,aminalandcarbamate).Sincethefinalmaterialresultsfromthepackingofoligomersthatwerethemselvesspontaneouslyassembledfromelementaryunitsthroughthereversibleformationofcovalentbonds,thissupramolecularsolidisintheclassofwhathavebeendubbeddynamicmaterialsbyLehn.1517Thisparticulardynamicmaterialpossessesoriginalproperties:boththematerialanditsconstitutiveoligomersdissociateuponCO2departureinacooperativemanner,andtheassemblyprocessisfoundtobeextremelyselectiveintermsofbuildingblockincorporation.18,19Bothfeatures(reversibilityandselectivity)aredesirableinthecontextofCO2captureanduse,aswellasforselectiveextractionofvaluablemoleculesfromwaste.20However,thematerialprecipitatesfromsolutionasaninsolublenano-crystallinepowder,whichisnotamenabletostandardmolecularlevelcharacterization.Toaddressthisproblemwepreviouslyusedsolid-stateNuclearMagneticResonance(NMR)toproposebasicstructuralfeaturesforthissupramolecularsystem.14
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Scheme1Doubleself-assemblyprocessleadingtothediscoveryofa3-componentdynamicmaterialbasedonCO2.(a)Elementarybuildingblockssuchaspolyaminesn(brownconnector)andpolyaldehydesX(orangehexagon)self-assembleinmethanolatRTunderairtoyield2-componentoligomers(b),mainlyX2n3capsules.InthecaseX=Aandn=2inthesameconditions,exposuretoCO2(bluearch)asathirdbuildingblockspontaneouslyyieldsthe3-componentsolubleoligodynablockA429(CO2)9.Thisself-assembledspeciesthenitselfspontaneouslyfurtherself-assemblesintothecorrespondinginsolubledynamicmaterialDMA2(CO2)asananocrystallinepowder(electronmicrograph,whitebar:100nm)(c).Heatingtoaround50CinducesCO2releaseanddisassemblyofthedynamicmaterialwhichconvertsbackintoA223.
Herewefurtherexplorethethree-dimensionalmolecularstructureofthenano-crystallinedynamicmaterialusinganNMRcrystallographyapproach,21,22andweevaluatethepertinenceofpowderX-raydiffraction(PXRD).Solid-stateNMRspectroscopycomplementsdiffractionmethodsandhasrecentlydevelopedintoaversatiletooltodeterminethestructuresofbothinorganicandmolecularsolids.2334IncombinationwithcrystalstructurepredictionmethodsandDFTchemicalshiftcalculations,NMRchemicalshiftshaverecentlybeenusedtodetermineddenovocrystalstructures.23Inparticularinthecontextofsupramolecularsolids,solid-stateNMRandDFTcalculationshavebeenusedtoexplorehydrogenbondingandmolecularstructureinorganicsupramolecularsystems35,36andtocharacterisestructuralfeaturesinMOFs,includingdeterminationofconformationchangesuponadsorptionortoobservethedynamiceventsthatgovernhostguestinteractions.3742Mostrecently,thesuperstructureofasubstitutedzeoliticimidazolateframework(ZIF)typeMOFwaselucidatedbycombiningsolid-stateNMR,PXRD,andDFTcalculationsofNMRparametersfrompotentialmodelstructures.43
Notablyveryrapidprogresshasrecentlybeenmadebycombiningsophisticatedspectralassignmentstrategieswithstate-of-the-artDensityFunctionalTheory(DFT)chemicalshiftcalculationmethods.
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