Atomically Precise Copper Cluster with Intensely Near-Infrared - Li et al. - Unknown - Unknown

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SupportingInformationAtomicallyPreciseCopperClusterwithIntenselyNear-InfraredLuminescenceandItsMechanismHaoLi,†HongshengZhai,§ChuanjunZhou,†YongboSong,*,†FengKe,†WenWuXu*,#andManzhouZhu*,††DepartmentofChemistryandCentreforAtomicEngineeringofAdvancedMaterials,AnhuiProvinceKeyLaboratoryofChemistryforInorganic/OrganicHybridFunctionalizedMaterials,KeyLaboratoryofStructureandFunctionalRegulationofHybridMaterialsofMinistryofEducation,AnhuiUniversity,Hefei,230601,People’sRepublicofChina.§SpectralMeasurementandApplicationofInfraredMaterialKeyLaboratoryofHenanProvince,SchoolofPhysics,HenanNormalUniversity,Xinxiang453007,People’sRepublicofChina.#DepartmentofPhysics,SchoolofPhysicalScienceandTechnology,NingboUniversity,Ningbo315211,People’sRepublicofChina.MaterialsAllreagentsarecommerciallyavailableanduseddirectlywithoutfurtherpurification.CuCl(99.8%),4-tert-butylthiophenol(98%),tetraoctylammoniumbromide(TOAB,98%),triphenylphosphine(PPh3,99%),sodiumborohydride(99.99%),chloroform(HPLCgrade,≥99.9%),methanol(HPLCgrade,≥99.9%),n-hexane(HPLCgrade,≥99.9%).Allglasswarewascleanedwithaquaregia(HCl:HNO3=3:1,v:v)andwashedthoroughlywithpurewaterbeforeused.Synthesisofthe[Cu11(TBBT)9(PPh3)6](SbF6)2cluster.Thewholereactionprocessiscarriedoutatroomtemperature.100mgtetraoctylammoniumbromideand40mgCuClweredissolvedinamixedsolventofchloroform(15mL)andmethanol(10mL)ina100mLroundbottomflaskatvigorouslystirred(~1200rpm).Afterthat,100mgtriphenylphosphinewasaddedintoabovesolution.After30mins,70uL4-tert-butylbenzenethiolwasdirectlyaddedtotheabovesolution.30minslater,5mLaqueoussolutionof50mgNaBH4wasrapidlyadded.24hourslater,theaqueoussolutionwasremoved,and100mgNaSbF6dissolvedin5mLmethanolwasaddedintotheorganicsolution.Theorganicsolutionwasdriedbyrotaryevaporationandwashedseveraltimeswithmethanoltoremovetheresidualligandsandby-products.Finally,theyellowcrystalwasobtainedbyn-hexanediffusionintothechloroformsolutionforoneweek.S1

1SynthesisoftheCu(I)-SRcomplex.10mgCuCl2dissolvedin10mLmethanoland100μL4-tert-butylthiophenolweremixedin25mLroundbottomflaskundervigorouslystirring.After10mins,theorganicsolutionwasremovedbycentrifugation.Andthen,theproductwaswashedseveraltimeswithmethanoltoremovetheresidualligands.Finally,theCu(I)-SRcomplexwascollectedbycentrifugation.CharacterizationSinglecrystalX-raydiffractometer.SinglecrystalX-raydiffractiondatawascollectedonaBrukerD8VenturediffractometerwiththeGaK\αX-raysource(λ=1.34139Å).Ayellowishneedle-likecrystalwithdimensions0.1x0.03x0.02mmwasmounted.Datacollectionwasperformedat170K.UsingOlex2,1thestructurewassolvedwiththeShelXT2structuresolutionprogramusingIntrinsicPhasingandrefinedwiththeShelXL3refinementpackageusingLeastSquaresminimisation.AlltheCuandSatomswerefounddirectly.Remainingnon-hydrogenatomsweregeneratedviasubsequentdifferenceFouriersyntheses.Allthenon-hydrogenatomswererefinedanisotropically.Allthehydrogenatomsweresetingeometricallycalculatedpositionsandrefinedisotropicallyusingaridingmodel.ThediffuseelectrondensitiesresultingfromtheresidualsolventmoleculeswereremovedfromthedatasetusingtheSQUEEZEroutineofPLATONandrefinedfurtherusingthedatagenerated.Electrosprayionization(ESI)massspectrumwasperformedonWatersXEVOG2-XSQTofmassspectrometer.ThesamplesaredissolvedinamixturesolutionofCH2Cl2/CH3OH(v:v=1:1),whichisdirectlyinfusedintothechamberat10µL/minwithpositivemode.Thermogravimetricanalysis(TGA)wascarriedoutonathermogravimetricanalyzer(DTG-60H,ShimadzuInstrumentsInc.,Japan)ataheatingrateof10K·min−1inN2atmosphere.1HNMRwereperformedonaBrukerAvance™II400NMRinstrument.Thedatawascollectedwith~5mgclustersdissolvedin0.6mLCD2Cl2.Inductivelycoupledplasmamassspectrometry(ICP-MS)wasperformedbyThermoiCAPQICP-MS.PowderX-raydiffraction(XRD)patternwasobtainedonSmartLab9KWwithCuKαradiation.X-rayphotoelectronspectroscopy(XPS)measurementswereperformedonThermoESCALAB250equippedwithamonochromatedAlKα(1486.8eV)150WX-raysource,0.5mmcircularspotsize,afloodguntocounterchargingeffects,andtheS2

2analysischamberbasepressurelowerthan1×10−9mbar;datawerecollectedwithFAT=20eV.UV-visabsorptionspectrawererecordedonAgilent8453spectrophotometer.Crystalsaredissolvedinsolution.PhotoluminescencespectraweremeasuredonaHORIBAJYFluorolog3-tau.Absolutequantumyields(QYs)andemissionlifetimeweremeasuredonaHORIBAFluoroMax-4P.Calculation.Allgeometryoptimizationswereperformedusingdensityfunctionaltheory(DFT)asimplementedintheAmsterdamDensityFunctional(ADF)2017package.4,5TheBP86exchange-correlationfunctionalwasusedforthesecalculations.6,7ATZPbasissetandalargefrozenelectroncorewereusedtoascertaincompleteness.Generalizedgradientapproximation(GGA)functionalshavebeenemployedsuccessfullyincalculatinggeometricandelectronicstructures.Allstructuresareoptimizedinthegasphase.Reference:(1)Dolomanov,O.V.,Bourhis,L.J.,Gildea,R.J,Howard,J.A.K.&Puschmann,H.(2009),J.Appl.Cryst.42,339-341.(2)Sheldrick,G.M.(2015).ActaCryst.A71,3-8.(3)Sheldrick,G.M.(2015).ActaCryst.C71,3-8.(4)teVelde,G.;Bickelhaupt,F.M.;Baerends,E.J.;FonsecaGuerra,C.;vanGisbergen,S.J.A.;Snijders,J.G.;Ziegler,T.ChemistrywithADF.J.Comput.Chem.2001,22,931-967.(5)Aerends,E.J.;etal.ADF2017,Scm,TheoreticalChemistry;VrijeUniversiteit:Amsterdam(https://www.scm.com).(6)Becke,A.D.Density-FunctionalExchange-EnergyApproximationwithCorrectAsymptoticBehavior.Phys.Rev.A:At.,Mol.,Opt.Phys.1988,38,3098-3100.(7)Perdew,J.P.Density-FunctionalApproximationFortheCorrelationEnergyoftheInhomogeneousElectronGas.Phys.Rev.B:Condens.MatterMater.Phys.1986,33,8822-8824.S3

3FigureS1.TwoSbF6-ionsaccompaniedwithCu11cluster.FigureS2.Twopairsofenantiomersinunitcell.FigureS3.Comparisonofthecalculated(red)andexperimental(black)isotopedistributionpatternsof(A)[Cu11(TBBT)9(PPh3)5]2+and(B)[Cu11(TBBT)9(PPh3)4]2+.S4

4FigureS4.TGAcurveofCu11cluster.FigureS5.PXRDofCu11cluster.S5

5FigureS6.1HNMRofCu11clusterdissolvedinCD2Cl2.(*wasresiduarysolventpeakofn-hexane)FigureS7.ComparedwiththebindingenergyforCu2p3/2ofCu(I)-TBBTcomplexandCu11cluster.S6

6FigureS8.Thetemperature-dependedUV-visabsorptionspectraofCu11clusterinCH2Cl2solution.Note:thesuddenchangeinbaselineat180KisinducedbythesolidificationofCHCl2solution.FigureS9.Time-dependentUV-visabsorptionspectraofCu11clusteratroomtemperatureinCHCl3.FigureS10.UV-visopticalabsorptionspectrumofCu11clusterinsolidstate.S7

7FigureS11.TheemissionlifetimeofCu11clustersinCHCl3solution.FigureS12.EmissionspectraoftheCu11clusterinCHCl3solutionunderO2andN2atmospheres(excitedat430nm).FigureS13.TheemissiondecaylifetimeofCu11clusterat180K(A)and80K(B).S8

8FigureS14.TheelectrondensitiesofHOMOsandLUMOsin[Cu11(SPh)9(PPh3)6]2+.S9

9TableS1.CrystaldataandstructurerefinementforCu11.IdentificationcodeCu11EmpiricalformulaC197H208Cu11P6S9F12Sb2Formulaweight4220.58Temperature170.01KWavelength1.3418ÅCrystalsystemMonoclinicSpacegroupP21/na=26.564(2)Åα=90°Unitcelldimensionsb=26.682(2)Åβ=106.652(5)°c=33.045(3)Åγ=90°Volume22448(3)Å3Z4Density(calculated)1.249Mg/cm3Absorptioncoefficient0.323mm-1F(000)8612Crystalsize0.1x0.03x0.02mm3Thetarangefordatacollection2.856to55.290°-32<=h<=28,-32<=k<=32,Indexranges-40<=l<=40Reflectionscollected233199Independentreflections42387[R(int)=0.2430]Completenesstotheta=55.290°98.1%AbsorptioncorrectionSemi-empiricalfromequivalentsMax.andmin.transmission0.7508and0.2514Full-matrix-blockleast-squaresonRefinementmethodF2Data/restraints/parameters42387/1182/2124Goodness-of-fitonF21.326FinalRindices[I>2sigma(I)]R1=0.1948,wR2=0.4618Rindices(alldata)R1=0.2785,wR2=0.4984Largestdiff.peakandhole2.454and-2.715e.Å-3TableS2PhotophysicaldataofCu11clusteratroomtemperature.λex(nm)λem(nm)PLQYτav(μs)UV-visAbs.(nm)Solid45067522%1.3400Solution4306857%1.23400S10

10TableS3.CartesiancoordinatesofthegeometricallyoptimizedCu11(SPh)9(PPh3)6.AtomxyzCu7.151626.8876330.51370Cu7.293587.9663427.72904Cu3.992335.5943432.86177Cu7.5911510.9183530.73132Cu9.423044.6748928.20983Cu5.336094.8422129.26003Cu4.484068.6374930.45928Cu6.757584.6092625.73022Cu5.2710511.3529827.75897Cu1.568655.5780729.96054Cu4.323107.3949127.79570S7.624984.7145229.80788S8.209258.8259729.72928S5.3220410.8173830.06010S4.855595.2332527.00904S5.470587.3113832.11569S3.535164.5481730.78336S8.326276.1106426.67730S5.515039.1724426.84255S2.634417.6496629.38626P11.317243.3909028.37819P-0.701605.2209129.87607P9.0379512.4291031.68895P5.1269713.2404126.47704P6.812322.9408724.16626P3.319885.2986135.03070C4.700674.7549136.12718C6.517429.4231924.25006H7.441849.7551424.72163C5.226059.1516034.19121H4.162959.1572733.95303C4.2265511.9703130.92854C2.026002.3158726.51192H1.896411.2733826.80558C4.148268.5676623.03590H3.221238.2328522.56753C9.990088.6757129.49378C8.460202.2392723.72654C5.836881.4411524.62041C7.800753.1325133.59175H7.655703.4846334.61416C12.553183.5298927.01688S11

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