Solid state multicolor emission in substitutional solid solutions of metal-organic frameworks

Article abstract of DOI:10.1021/jacs.9b05191

Preparing crystalline materials that produce tunable organic-based multicolor emission is a challenge due to the inherent inability to control the packing of organic molecules in the solid state. Utilizing multivariate, high-symmetry metal-organic frameworks, MOFs, as matrices for organic-based substitutional solid solutions allows for the incorporation of multiple fluorophores with different emission profiles into a single material. By combining nonfluorescent links with dilute mixtures of red, green, and blue fluorescent links, we prepared zirconia-Type MOFs and found that the bulk materials exhibit features of solution-like fluorescence. Our study found that MOFs with a fluorophore link concentration of around 1 mol % exhibit fluorescence with decreased inner filtering, demonstrated by changes in spectral profiles, increased quantum yields, and lifetime dynamics expected for excited-state proton-Transfer emitters. Our findings enabled us to prepare organic-based substitutional solid solutions with tunable chromaticity regulated only by the initial amounts of fluorophores. These materials emit multicolor and white light with high quantum yields (-2-14%), high color-rendering indices (>93), long shelf life, and superb hydrolytic stability at ambient conditions.

Full text of DOI:10.1021/jacs.9b05191

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Article
Solid state multicolor emission in substitutional
solid solutions of metal-organic frameworks
Wesley J. Newsome, Suliman Ayad, Jesus Cordova, Eric W. Reinheimer, Andres
D Campiglia, James K. Harper, Kenneth Hanson, and Fernando J. Uribe-Romo
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b05191 • Publication Date (Web): 20 Jun 2019
Downloaded from http://pubs.acs.org on June 20, 2019
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Solid state multicolor emission in substitutional solid solutions of
metal-organic frameworks
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1§
2§
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1ꢀ
WesleyꢀJ.ꢀNewsome, ꢀSulimanꢀAyad, ꢀJesusꢀCordova, ꢀEricꢀW.ꢀReinheimer, ꢀAndresꢀD.ꢀCampiglia,
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2*
1*
JamesꢀK.ꢀHarper, ꢀKennethꢀHanson, ꢀFernandoꢀJ.ꢀUribe-Romo. ꢀ
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DepartmentꢀofꢀChemistry,ꢀUniversityꢀofꢀCentralꢀFlorida,ꢀ4111ꢀLibraꢀDr.ꢀRm.ꢀ251ꢀPSB,ꢀOrlando,ꢀFLꢀ32816-2366,ꢀUSA.ꢀ
DepartmentꢀofꢀChemistryꢀ&ꢀBiochemistry,ꢀFloridaꢀStateꢀUniversity,ꢀ95ꢀChieftanꢀWay,ꢀTallahassee,ꢀFLꢀ32306-4390,ꢀUSA.ꢀ
RigakuꢀAmericasꢀCorporation,ꢀ9009ꢀNewꢀTrailsꢀDr.,ꢀTheꢀWoodlands,ꢀTXꢀ77381,ꢀUSA.ꢀ
§
ꢀ=ꢀEqualꢀcontribution.ꢀ
Whiteꢀlightꢀemission,ꢀStructure-propertyꢀrelationship,ꢀBroadbandꢀfluorescenceꢀ
ꢀ
ABSTRACT:ꢀPreparingꢀcrystallineꢀmaterialsꢀthatꢀproduceꢀtunableꢀorganic-basedꢀmulticolorꢀemissionꢀisꢀaꢀchallenge,ꢀdueꢀtoꢀ
theꢀinherentꢀinabilityꢀtoꢀcontrolꢀtheꢀpackingꢀofꢀorganicꢀmoleculesꢀinꢀtheꢀsolidꢀstate.ꢀUtilizingꢀmultivariate,ꢀhighꢀsymmetryꢀ
metal-organicꢀframeworks,ꢀMOFs,ꢀasꢀmatricesꢀforꢀorganic-basedꢀsubstitutionalꢀsolidꢀsolutionsꢀallowsꢀforꢀtheꢀincorporationꢀ
ofꢀmultipleꢀfluorophoresꢀwithꢀdifferentꢀemissionꢀprofilesꢀ intoꢀ aꢀ singleꢀ material.ꢀByꢀcombiningꢀnon-fluorescentꢀlinksꢀwithꢀ
diluteꢀmixturesꢀofꢀred,ꢀgreen,ꢀandꢀblueꢀfluorescentꢀlinksꢀweꢀpreparedꢀzirconia-typeꢀMOFsꢀandꢀfoundꢀthatꢀtheꢀbulkꢀmaterialsꢀ
exhibitꢀfeaturesꢀofꢀsolution-likeꢀfluorescence.ꢀOurꢀstudyꢀfoundꢀthatꢀMOFsꢀwithꢀfluorophoreꢀlinkꢀconcentrationꢀofꢀaroundꢀ1ꢀ
mol%ꢀexhibitꢀfluorescenceꢀwithꢀdecreasedꢀinnerꢀfiltering,ꢀdemonstratedꢀbyꢀchangesꢀinꢀspectralꢀprofiles,ꢀincreasedꢀquantumꢀ
yields,ꢀandꢀlifetimeꢀdynamicsꢀexpectedꢀforꢀexcitedꢀstateꢀprotonꢀtransferꢀemitters.ꢀOurꢀfindingsꢀenabledꢀusꢀtoꢀprepareꢀorgan-
ic-basedꢀ substitutionalꢀ solidꢀ solutionsꢀ withꢀ tunableꢀ chromaticityꢀ regulatedꢀ onlyꢀ byꢀ theꢀ initialꢀ amountsꢀ ofꢀ fluorophores.ꢀ
Theseꢀmaterialsꢀemitꢀmulticolorꢀandꢀwhiteꢀlightꢀwithꢀhighꢀquantumꢀyieldsꢀ(~2-14%),ꢀhighꢀcolorꢀrenderingꢀindicesꢀ(>93),ꢀ
longꢀshelfꢀlife,ꢀandꢀsuperbꢀhydrolyticꢀstabilityꢀatꢀambientꢀconditions.ꢀ
ꢀ
ꢀ
Introductionꢀ
matchingꢀ isꢀ aꢀ non-trivialꢀ task.8-9ꢀ Second,ꢀ organicꢀ com-
Multicolorꢀ emissionꢀ inꢀ solutionsꢀ isꢀ aꢀ phenomenonꢀ thatꢀ
poundsꢀ tendꢀ toꢀ formꢀ lowꢀ symmetryꢀ andꢀ unpredictableꢀ
occursꢀ inꢀ aꢀ systemꢀ ofꢀ multipleꢀ emitters,ꢀ whereꢀ theꢀ bulkꢀ
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crystalꢀpackings, ꢀwhichꢀmakesꢀtheirꢀbulkꢀcrystallographicꢀ
characterizationꢀ aꢀ challenge.ꢀ Third,ꢀ asꢀ mentionedꢀ above,ꢀ
mixturesꢀ ofꢀ organicꢀ compoundsꢀ phaseꢀ separateꢀ duringꢀ
crystallization,ꢀsoꢀhomogeneousꢀincorporationꢀofꢀsolutesꢀisꢀ
notꢀ ensured.ꢀDespiteꢀ theseꢀ challenges,ꢀ preparationꢀ ofꢀ or-
ganic-basedꢀSSSꢀwithꢀtunableꢀfluorescenceꢀwouldꢀallowꢀforꢀ
preparingꢀcrystallineꢀmaterialsꢀthatꢀtakeꢀadvantageꢀofꢀtheꢀ
inherentꢀtunabilityꢀofꢀmolecularꢀemitters.ꢀ
fluorescenceꢀ ofꢀ aꢀ solutionꢀ isꢀ theꢀ resultꢀ ofꢀ theꢀ combinedꢀ
emissionꢀ ofꢀ eachꢀ emitter.1-2ꢀ Inꢀ liquidꢀ solutionsꢀ ofꢀ diluteꢀ
organicꢀ fluorophores,ꢀ thisꢀ phenomenonꢀ isꢀ easilyꢀ con-
trolled,ꢀbecauseꢀsolutionsꢀwithꢀexactꢀconcentrationsꢀcanꢀbeꢀ
prepared.ꢀInꢀtheꢀcrystallineꢀsolid-stateꢀ(i.e.,ꢀexcludingꢀpol-
ymerꢀblendsꢀandꢀglasses),ꢀorganic-basedꢀ multicolorꢀ emis-
sionꢀ isꢀ moreꢀ challengingꢀ toꢀ produce,ꢀ becauseꢀ whenꢀ theꢀ
solventꢀ isꢀ removed,ꢀ mixturesꢀ ofꢀ organicꢀ fluorophoresꢀag-
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gregate, ꢀphaseꢀseparate,ꢀandꢀquench,ꢀproducingꢀhetero-
geneousꢀsolidꢀmixturesꢀwithꢀunpredictableꢀfluorescence.ꢀAꢀ
strategyꢀ toꢀ produceꢀ organic-basedꢀ crystalsꢀ withꢀ tunableꢀ
bulkꢀ multicolorꢀ emissionꢀ isꢀ byꢀ adaptingꢀ theꢀ solid-stateꢀ
chemistryꢀ conceptꢀ ofꢀ substitutionalꢀ solidꢀ solutionsꢀ (SSS).ꢀ
SSSꢀareꢀcrystalsꢀthatꢀformꢀwhenꢀaꢀsoluteꢀatomꢀ(Figureꢀ1a)ꢀ
isꢀincorporatedꢀintoꢀaꢀuniformꢀcrystallineꢀmatrix,ꢀsubstitut-
ingꢀ someꢀ ofꢀtheꢀ matrixꢀatoms,ꢀ soꢀtheꢀ soluteꢀ isꢀ effectivelyꢀ
Multivariateꢀmetal-organicꢀframeworksꢀ(MTVꢀMOFs)ꢀareꢀaꢀ
sub-classꢀofꢀMOFsꢀwhereꢀorganicꢀlinksꢀofꢀvariedꢀfunctional-
izationꢀareꢀincorporatedꢀintoꢀaꢀsingleꢀphaseꢀMOF. ꢀTheseꢀ
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typesꢀofꢀMOFsꢀareꢀanꢀattractiveꢀplatformꢀforꢀmakingꢀmulti-
colorꢀ emittingꢀ crystalsꢀ becauseꢀ theꢀ crystallineꢀ arrange-
mentꢀofꢀtheꢀorganicꢀlinksꢀisꢀdictatedꢀbyꢀtheꢀstructureꢀofꢀtheꢀ
MOF.ꢀWhenꢀconsideringꢀhigh-symmetryꢀMOFs,ꢀtheꢀorganicꢀ
linksꢀ willꢀ alsoꢀ arrangeꢀ inꢀ aꢀ highꢀ symmetryꢀ environmentꢀ
despiteꢀtheirꢀdifferencesꢀinꢀchemicalꢀfunctionalityꢀ(Figureꢀ
5
dissolvedꢀwithinꢀtheꢀaverageꢀunitꢀcell. ꢀApplicationꢀofꢀthisꢀ
conceptꢀinꢀinorganicꢀmaterialsꢀhasꢀallowedꢀforꢀfine-tunedꢀ
controlꢀofꢀphysicalꢀpropertiesꢀofꢀmaterialsꢀforꢀapplicationsꢀ
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b). ꢀHere,ꢀweꢀdemonstrateꢀthatꢀutilizingꢀhigh-symmetryꢀ
multivariateꢀMOFsꢀasꢀmatricesꢀforꢀorganic-basedꢀSSSꢀena-
blesꢀtheꢀpreparationꢀofꢀcrystallineꢀmulticolorꢀemittingꢀma-
terials.ꢀ Byꢀ forcingꢀ theꢀ organicꢀ linksꢀ toꢀ arrangeꢀ inꢀ highꢀ
symmetryꢀenvironments,ꢀ
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suchꢀasꢀlasers ꢀandꢀblueꢀLEDs. ꢀInꢀtheꢀcaseꢀofꢀorganicꢀmate-
rials,ꢀhowever,ꢀtheꢀconceptꢀofꢀpreparingꢀSSSꢀdoesꢀnotꢀgen-
erallyꢀapplyꢀforꢀseveralꢀreasons.ꢀFirst,ꢀunlikeꢀatoms,ꢀorgan-
icꢀmoleculesꢀareꢀnon-spherical,ꢀsoꢀmatrix-dopantꢀ
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ꢀ
TheꢀMOFꢀmatrixꢀutilizedꢀhereꢀconsistsꢀonꢀtheꢀzirconia-typeꢀ
PPPP-PIZOFꢀMOFꢀ(FigureꢀS1),ꢀanꢀinterwovenꢀface-centeredꢀ
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cubicꢀnetworkꢀ(spaceꢀgroupꢀFd-3m) ꢀꢀbuiltꢀwithꢀtetrame-
thylꢀ quarterphenyldicarboxylateꢀ (Figureꢀ 1c)ꢀ thatꢀ isꢀ non-
fluorescentꢀ inꢀ theꢀ visibleꢀ region.ꢀ Thisꢀ MOFꢀ typeꢀ isꢀ waterꢀ
stableꢀandꢀallowsꢀ forꢀtheꢀ incorporationꢀ ofꢀ linksꢀ ofꢀ variedꢀ
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nature. ꢀBasedꢀonꢀESPTꢀdyesꢀdesignedꢀbyꢀParkꢀetꢀal.,ꢀtheꢀ
multivariateꢀ linksꢀ areꢀ composedꢀ ofꢀ quarterphenylꢀ chainsꢀ
bearingꢀ 1,2-diarylphenanthro[9,10-d]imidazoleꢀ fluoro-
phores.14-15ꢀThisꢀmoietyꢀwasꢀutilizedꢀasꢀaꢀtemplateꢀforꢀitsꢀ
stabilityꢀtoꢀMOFꢀsyntheticꢀconditions,ꢀhighꢀquantumꢀyield,ꢀ
andꢀeaseꢀofꢀcolorꢀvariabilityꢀthroughꢀsynthesis.ꢀWhenꢀtheꢀ
arylꢀatꢀtheꢀ2ꢀpositionꢀisꢀanꢀo-phenolꢀderivative,ꢀtheꢀdyeꢀcanꢀ
existꢀasꢀanꢀenolꢀorꢀketoꢀtautomerꢀ(Figureꢀ1d)ꢀbyꢀtransfer-
ringꢀtheꢀphenolicꢀprotonꢀtoꢀtheꢀunsubstitutedꢀnitrogenꢀofꢀ
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theꢀimidazoleꢀring. ꢀInꢀtheꢀgroundꢀstate,ꢀtheseꢀdyesꢀexistꢀinꢀ
theꢀ enolꢀtautomer.ꢀ Afterꢀexcitation,ꢀaꢀ protonꢀ transferꢀ canꢀ
occurꢀproducingꢀtheꢀexcitedꢀstateꢀketoꢀformꢀthatꢀinducesꢀaꢀ
largeꢀ apparentꢀ Stokesꢀ shift,ꢀ thatꢀ variesꢀ accordingꢀ toꢀ theꢀ
molecularꢀstructureꢀofꢀtheꢀphenol.ꢀAsꢀsuch,ꢀanꢀunsubstitut-
edꢀphenolꢀhasꢀaꢀsmallꢀshift,ꢀemittingꢀinꢀtheꢀblue,ꢀaddingꢀaꢀ
phenylꢀ groupꢀ shiftsꢀemissionꢀtoꢀgreen,ꢀandꢀ changingꢀtoꢀ aꢀ
naphtholꢀgroupꢀfurtherꢀshiftsꢀemissionꢀtoꢀred.ꢀAfterꢀrelax-
ingꢀviaꢀemission,ꢀtheꢀdyeꢀreadilyꢀrevertsꢀtoꢀtheꢀenolꢀform.ꢀ
ThisꢀlargeꢀapparentꢀStokesꢀshiftꢀisꢀadvantageousꢀforꢀmixedꢀ
fluorophoreꢀ systemsꢀ becauseꢀ itꢀ allowsꢀ forꢀ singleꢀ wave-
lengthꢀexcitationꢀofꢀtheꢀhighꢀenergyꢀꢀ
ꢀ
Figure 1 (a) Scheme of inorganic-based substitutional solid solu-
tion (b) Scheme of organic-based substitutional solid solution
formation in MOFs. (c) Organic links used in this study. (d) Ex-
cited state proton transfer (ESPT) enol and keto tautomers.
aꢀhigherꢀlevelꢀofꢀsyntheticꢀcontrolꢀcanꢀbeꢀachieved,ꢀbecauseꢀ
theseꢀMTVꢀMOFsꢀcircumventꢀtheꢀproblemsꢀassociatedꢀwithꢀ
organic-basedꢀSSSꢀ (seeꢀ above).ꢀ Alsoꢀ usingꢀ highꢀ symmetryꢀ
MOFsꢀ(e.g.ꢀcubic)ꢀfacilitatesꢀcrystallographicꢀcharacteriza-
tionꢀviaꢀcrystalꢀsimulationsꢀandꢀpowderꢀdiffractometry.ꢀWeꢀ
demonstrateꢀ thatꢀ incorporationꢀ ofꢀ linksꢀ thatꢀ containꢀred,ꢀ
greenꢀandꢀblueꢀ(RGB)ꢀfluorescentꢀmoietiesꢀ(Figureꢀ1b)ꢀintoꢀ
aꢀnon-fluorescent,ꢀhigh-symmetryꢀMOF,ꢀresultsꢀinꢀtheꢀfor-
mationꢀ ofꢀ fluorescent,ꢀ organic-basedꢀ SSS.ꢀ Theꢀ observedꢀ
organicꢀSSSꢀbehaviorꢀallowsꢀtunableꢀmulticolorꢀemissionꢀinꢀ
bulkꢀcrystalsꢀwithꢀemissiveꢀpropertiesꢀdictatedꢀexclusivelyꢀ
byꢀtheꢀinputꢀconcentrationꢀofꢀRGBꢀfluorophoreꢀlinks,ꢀpro-
ducingꢀmaterialsꢀthatꢀfluoresceꢀwithꢀmanyꢀdifferentꢀcolors,ꢀ
includingꢀ whiteꢀ light,ꢀwithꢀ easy-to-tuneꢀ colorꢀ parametersꢀ
(e.g.ꢀ chromaticityꢀ andꢀwhite-lightꢀ temperature),ꢀandꢀ veryꢀ
highꢀ colorꢀ renderingꢀ indices.ꢀ Theꢀ preparedꢀ materialsꢀ re-
tainꢀ theirꢀ crystallinityꢀ atꢀ roomꢀ temperatureꢀ forꢀ monthsꢀ
underꢀnormalꢀlaboratoryꢀconditions,ꢀandꢀevenꢀafterꢀdirectꢀ
exposureꢀ toꢀ water.ꢀ Weꢀ foundꢀ thatꢀ dilutionꢀ ofꢀ fluorescentꢀ
linksꢀatꢀaroundꢀ1.0ꢀmol%ꢀdisplayedꢀtypicalꢀsolutionꢀbehav-
ior,ꢀ includingꢀ decreasedꢀ innerꢀ filtering,ꢀ highꢀ quantumꢀ
yields,ꢀ tunableꢀ chromaticities,ꢀ excitation-emissionꢀ inde-
pendence,ꢀ concentrationꢀ dependentꢀ energyꢀ transfer,ꢀ asꢀ
wellꢀ asꢀ emissionꢀ phenomenaꢀ expectedꢀ fromꢀ theꢀ fluoro-
phores,ꢀsuchꢀasꢀexcited-stateꢀprotonꢀtransferꢀ(ESPT).ꢀ
Figure 2 (a) Powder X-ray diffraction (PXRD) patterns of NF
and RGB-containing MOFs, indicating their isoreticular nature.
(b) Substitutional input-output plot for 3 sets of single fluorophore
MOFs with x in mol%.
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Figure 3 (a) Overlay of toluene-solvated fluorophore esters (compounds S7, S13, and S16, dashed lines) and x = 10 mol% input single
fluorophore MOFs (solid lines). (b) CIE chromaticity coordinates of prepared x = 10 mol% MOFs (open circles) and solvated ester links
(closed circles), and optical image of MOF powders and solvated links under UV light. (c-e) Emission profiles of B, G, and R MOFs, re-
spectively at varied dilution (0.1 ≤ x ≤ 10 mol%) indicating their excited-state lifetimes and quantum yields (λex = 365 nm).
enolꢀ formꢀ andꢀ emissionꢀ fromꢀ theꢀ lowꢀ energyꢀ ketoꢀ formꢀ
withꢀ minimalꢀ spectralꢀ overlap.16-17ꢀFurthermore,ꢀcovalentꢀ
attachmentꢀ ofꢀ diaryl-phenanthroimidazoleꢀ toꢀ theꢀ quater-
phenylꢀlinksꢀensuresꢀthatꢀfluorophoresꢀwillꢀnotꢀdiffuseꢀorꢀ
linksꢀ inꢀ theꢀ SSS,ꢀ previousꢀ workꢀ onꢀ high-symmetryꢀ MTVꢀ
MOFsꢀhasꢀshownꢀthatꢀtheꢀdistributionꢀofꢀtheꢀMTVꢀlinksꢀisꢀ
,ꢀ
highlyꢀdependentꢀonꢀtheꢀdilutionꢀrangeꢀofꢀtheꢀdopantꢀlink. ꢀꢀ
Inꢀourꢀcase,ꢀhighꢀfluorophoreꢀdilutionꢀlikelyꢀresultsꢀinꢀMOFꢀ
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leachꢀoutꢀofꢀtheꢀsolid.
ꢀTheꢀSSSꢀwereꢀpreparedꢀusingꢀtheꢀ
withꢀhomogeneousꢀdistribution, ꢀwithꢀtheꢀ10ꢀmol%ꢀMOFsꢀ
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multivariateꢀlinksꢀshownꢀinꢀFigureꢀ1b,ꢀhereinꢀreferredꢀtoꢀasꢀ
NFꢀ(non-fluorescent),ꢀRꢀ(red),ꢀGꢀ(green),ꢀandꢀBꢀ(blue).ꢀꢀꢀ
potentiallyꢀformingꢀalternatingꢀapportionments. ꢀFurtherꢀ
studiesꢀusingꢀmultidimensionalꢀsolid-stateꢀNMRꢀonꢀisotop-
icallyꢀenrichedꢀMOFsꢀwillꢀprovideꢀthisꢀinformation.ꢀNone-
theless,ꢀconsistentꢀandꢀreproducibleꢀfluorescenceꢀwasꢀob-
servedꢀ inꢀ theꢀ bulk,ꢀ indicatingꢀ littleꢀ effectꢀ fromꢀ theꢀ linksꢀ
distribution.ꢀ
ResultsꢀandꢀDiscussionꢀ
CrystallineꢀsingleꢀfluorophoreꢀMOFsꢀofꢀNFꢀwithꢀR,ꢀG,ꢀorꢀBꢀ
producedꢀsolidsꢀsamplesꢀwithꢀformulasꢀZr
,ꢀ Zr (OH) [G ,ꢀ andꢀ Zr (OH)
substitutionalꢀ inputꢀ xꢀ valuesꢀ betweenꢀ 0.10ꢀ andꢀ 10ꢀ mol%ꢀ
SeeꢀSIꢀforꢀmethods).ꢀForꢀsimplicity,ꢀsamplesꢀwithꢀaꢀsingleꢀ
fluorophoreꢀ willꢀ beꢀ referredꢀ toꢀ asꢀ x%-fluorophore,ꢀ i.e.,ꢀ
0%-B,ꢀ10%-G,ꢀandꢀ10%-RꢀforꢀMOFsꢀwithꢀaꢀ10%ꢀfluoro-
6
O
4
(OH)
4
[R
x
NF1-
]
x 6
6
O
4
4
NF1-x]
x 6
6
O
4
4
[B NF1-x]
x 6
ꢀ withꢀ
Despiteꢀ havingꢀ similarꢀ absorptionꢀ profilesꢀ (Figureꢀ S2),ꢀ
uponꢀexcitationꢀatꢀ365ꢀnm,ꢀMOFsꢀmadeꢀwithꢀ10%-R,ꢀ10%-
G,ꢀandꢀ10%-B,ꢀexhibitꢀsolid-stateꢀemissionꢀmaximaꢀatꢀ430,ꢀ
510,ꢀandꢀ630ꢀnmꢀ(Figureꢀ3a),ꢀrespectively,ꢀwithꢀrelativelyꢀ
highꢀ colorꢀ purityꢀ (Figureꢀ 3b).ꢀ Theꢀ emissionꢀ profilesꢀ ofꢀ
theseꢀ MOFsꢀ areꢀ drasticallyꢀ differentꢀ thanꢀ theꢀ neatꢀ solidꢀ
linkersꢀ(FigureꢀS3).ꢀInꢀcontrast,ꢀtheꢀlowꢀenergyꢀketoꢀemis-
sionꢀinꢀtheꢀMOFsꢀcloselyꢀresemblesꢀthatꢀofꢀtheꢀesterꢀformsꢀ
ofꢀ theꢀ RGBꢀ linksꢀ solvatedꢀ inꢀ tolueneꢀ (Figureꢀ 3a,ꢀ dashedꢀ
lines),ꢀ suggestingꢀ thatꢀ theꢀ poreꢀ microenvironmentꢀ ofꢀ theꢀ
MOFꢀ moreꢀ closelyꢀresemblesꢀtheꢀtoluene-solvated,ꢀ ratherꢀ
thanꢀneatꢀsolidsꢀofꢀtheꢀlinker.ꢀꢀ
(
1
phoreꢀ input.ꢀ Allꢀ samplesꢀ wereꢀ preparedꢀ utilizingꢀ sol-
13
vothermalꢀ MOFꢀ crystallizationꢀ conditions ꢀ andꢀ exhibitedꢀ
theꢀ sameꢀ powderꢀ X-rayꢀ diffractionꢀ (PXRD)ꢀ patternꢀ ofꢀ theꢀ
pureꢀNFꢀMOFꢀ(Figureꢀ2a).ꢀPredictableꢀandꢀadjustableꢀlinkerꢀ
incorporationꢀ wasꢀ demonstratedꢀ fromꢀ theꢀ syntheticꢀ in-
put/structuralꢀoutputꢀplotꢀshownꢀinꢀFigureꢀ2bꢀwithꢀoutputꢀ
1
compositionꢀvaluesꢀdeterminedꢀbyꢀsolutionꢀ HꢀNMRꢀofꢀdi-
gestedꢀ MOFꢀ samplesꢀ (Sectionꢀ S6).ꢀ Attemptsꢀ toꢀ prepareꢀ
MOFsꢀ withꢀ higherꢀ fluorophoreꢀcontentꢀ (>10ꢀ mol%)ꢀ wereꢀ
unsuccessful,ꢀ producingꢀ amorphous,ꢀ non-porousꢀ solidsꢀ
withꢀ inconsistentꢀ fluorophoreꢀ content.ꢀ Thisꢀ observationꢀ
indicatesꢀthatꢀtheꢀMOFꢀmatrixꢀhasꢀaꢀlimitedꢀtoleranceꢀforꢀ
stericallyꢀcrowdedꢀlinks.ꢀFurthermore,ꢀitꢀalsoꢀsuggestsꢀthatꢀ
itꢀ isꢀ unlikelyꢀ thatꢀ aꢀ mix-phaseꢀ MOFꢀ compositeꢀ isꢀ formedꢀ
Theꢀfluorophoreꢀmimicsꢀliquid-phaseꢀsolutionꢀbehaviorꢀinꢀ
thatꢀtheꢀRGBꢀlinksꢀshowꢀconcentrationꢀdependentꢀchangesꢀ
inꢀ theꢀ emissionꢀ profilesꢀ forꢀ allꢀ threeꢀ fluorophoreꢀ MOFsꢀ
(Figureꢀ3c-e).ꢀTheseꢀchangesꢀareꢀmostꢀnotableꢀinꢀRꢀandꢀG
ꢀ
containingꢀMOFs,ꢀwhereꢀthereꢀisꢀaꢀgradualꢀincreaseꢀinꢀtheꢀ
highꢀ energyꢀ enolꢀemissionꢀ withꢀ decreasingꢀconcentrationꢀ
andꢀaꢀ shiftꢀ inꢀtheꢀCIEꢀ (Commissionꢀ Internationaleꢀ deꢀ l'E-
clairage)ꢀchromaticityꢀcoordinatesꢀfromꢀtheꢀredꢀandꢀgreenꢀ
(e.g.,ꢀclusteredꢀRGBꢀMOFꢀcrystalsꢀmixedꢀwithꢀpureꢀNFꢀMOFꢀ
crystals).ꢀ Regardingꢀ theꢀ homogeneityꢀ ofꢀ theꢀ fluorescentꢀ
ACS Paragon Plus Environment

Journal of the American Chemical Society
regionsꢀ towardsꢀ theꢀ blueꢀ portionꢀ ofꢀ theꢀ diagramꢀ (Figureꢀ
Page 4 of 9
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S4).ꢀForꢀBꢀandꢀR,ꢀtheꢀspectralꢀchangesꢀareꢀaccompaniedꢀbyꢀ
anꢀemissionꢀlifetimeꢀandꢀquantumꢀyieldꢀincreaseꢀfromꢀxꢀ=ꢀ
10ꢀtoꢀ1.0ꢀmol%ꢀ(Figureꢀ3cꢀandꢀ3e,ꢀTableꢀS3).ꢀTheseꢀobser-
2
1
vationsꢀ areꢀ consistentꢀ withꢀ anꢀ energyꢀ transferꢀ event ꢀ
whereꢀ spectralꢀ overlapꢀ betweenꢀ enolꢀ emissionꢀ andꢀ enolꢀ
absorptionꢀinhibitsꢀtheꢀhigherꢀenergyꢀlightꢀfromꢀexitingꢀtheꢀ
solid.ꢀAꢀsimilarꢀeffectꢀcanꢀbeꢀobservedꢀinꢀconcentratedꢀso-
lutionsꢀ butꢀ isꢀ presumablyꢀ greatlyꢀ enhancedꢀ byꢀ theꢀ highꢀ
2
2
localꢀconcentrationꢀofꢀtheꢀfluorophoresꢀinꢀtheꢀMOF. ꢀMoni-
toringꢀ theꢀ excitedꢀ stateꢀ dynamicsꢀ inꢀ theꢀ MOFꢀ usingꢀ sub-
nanosecondꢀ transientꢀ absorptionꢀ measurementsꢀ willꢀ beꢀ
necessaryꢀ toꢀ definitivelyꢀ establishꢀ anꢀ energyꢀ transferꢀ
mechanism.ꢀRegardless,ꢀtheꢀsimilarityꢀinꢀlifetimeꢀandꢀquan-
tumꢀyieldꢀbetweenꢀ1.0%-Bꢀandꢀ0.1%-B,ꢀasꢀwellꢀas,ꢀ1.0%-
Rꢀandꢀ0.1%-Rꢀ(Figureꢀ 3cꢀandꢀ3e)ꢀsuggestsꢀthatꢀtheꢀinnerꢀ
filteringꢀ effectꢀ isꢀ minimalꢀ atꢀ concentrationsꢀ ofꢀ xꢀ =ꢀ 1.0ꢀ
mol%.ꢀTheseꢀconcentrationsꢀofꢀfluorophoreꢀresultꢀinꢀMOFsꢀ
withꢀ quantumꢀ yieldsꢀwhichꢀareꢀ upꢀtoꢀanꢀ orderꢀ ofꢀ magni-
tudeꢀgreaterꢀthanꢀpreviouslyꢀpreparedꢀbroadbandꢀemittingꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
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8
9
0
1
2
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0
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9
0
2
3-25
MOFs.
ꢀandꢀareꢀsimilarꢀtoꢀtheꢀsolubleꢀesterꢀformsꢀofꢀtheꢀ
linkersꢀinꢀaꢀtolueneꢀsolutionꢀ(TableꢀS2).ꢀꢀ
Thisꢀdilutionꢀcanꢀbeꢀinterpretedꢀinꢀtermsꢀofꢀmolarꢀconcen-
trationꢀ ofꢀ theꢀ linksꢀ inꢀ theꢀ MOF,ꢀ sinceꢀ [links]maxꢀ =ꢀ 1.34ꢀ Mꢀ
(
singleꢀcrystalꢀanalysisꢀofꢀNFꢀMOFꢀevidencesꢀ48ꢀlinksꢀperꢀ
ꢀ
3
unitꢀcellꢀwithꢀaꢀcellꢀvolumeꢀofꢀ58,400ꢀÅ ,ꢀequivalentꢀtoꢀ1.34ꢀ
mollinksꢀdm ).ꢀAsꢀsuch,ꢀ10%-B,ꢀ1.0%-B,ꢀandꢀ0.1%-Bꢀhaveꢀ
Figure 4 Two component SSS MOFs: (Top) Optical images of
samples under λex = 365 nm indicating their fluorophore composi-
tion, (middle) emission profiles with λex = 365 nm, and (bottom)
CIE chromaticity coordinates of mixtures of R and B (left), and
mixtures of G and B (right).
-3
molarꢀconcentrationsꢀofꢀ[B]ꢀ=ꢀ134ꢀmM,ꢀ13.4ꢀmM,ꢀandꢀ1.34ꢀ
mM,ꢀ respectively.ꢀ Theseꢀ molarityꢀ valuesꢀ forꢀ 1.0%-Bꢀ andꢀ
0.1%-Bꢀ fallꢀ closeꢀ toꢀ aꢀ dilutionꢀ rangeꢀ withꢀ reducedꢀ innerꢀ
filtering,ꢀ andꢀ theꢀ 10%-Bꢀ resemblesꢀ aꢀ concentratedꢀ solu-
tionꢀwhereꢀtheꢀemissionꢀisꢀdominatedꢀbyꢀthisꢀinnerꢀfilter-
ing.ꢀꢀ
Theꢀ three-fluorophoreꢀ systemꢀ withꢀ aꢀ compositionꢀ ofꢀ
Zr (OH) (R NF1-y,ꢀ exhibitedꢀ emissionꢀ profilesꢀ
6
O
4
4
x
G
1-2x x y
B )
thatꢀ dependꢀ onꢀ theꢀtotalꢀ fluorophoreꢀ concentrationꢀ y.ꢀ Asꢀ
expectedꢀforꢀyꢀ=ꢀ0.10,ꢀtheꢀemissionꢀ isꢀ stronglyꢀ dependentꢀ
onꢀ theꢀexcitationꢀ wavelengthꢀ (Figureꢀ S6-8)ꢀandꢀ generallyꢀ
dominatedꢀbyꢀyellowꢀemissionꢀ(Rꢀ+ꢀG)ꢀwithꢀminimalꢀhighꢀ
energyꢀcontributionꢀ (B)ꢀ dueꢀ toꢀ strongꢀ innerꢀ filterꢀ effects.ꢀ
Incorporationꢀ ofꢀ twoꢀ andꢀ threeꢀ fluorophoresꢀ resultedꢀ inꢀ
MOFsꢀthatꢀexhibitꢀ theꢀcombinedꢀemissionꢀ ofꢀeachꢀ fluoro-
phore.ꢀ Forꢀ Zr
6
O
4
(OH)
4
(R
B )
x 1-x y
NF1-y,ꢀ Zr
6
O
4
(OH)
4
(G
B
x 1-
)
x y
NF1-yꢀ withꢀ yꢀ =ꢀ 0.01,ꢀ underꢀ 365ꢀ nmꢀ excitation,ꢀ weꢀ ob-
servedꢀ aꢀ sumꢀ ofꢀ theꢀ individualꢀ componentsꢀ andꢀ aꢀ linearꢀ
transitionꢀfromꢀRꢀtoꢀBꢀorꢀGꢀtoꢀBꢀasꢀxꢀvariesꢀfromꢀ0.9ꢀtoꢀ0.5ꢀ
toꢀ0.1ꢀ(Figureꢀ4).ꢀTheꢀexcitation-emissionꢀmapsꢀ(FigureꢀS5)ꢀ
asꢀwellꢀasꢀCIEꢀcoordinateꢀdiagramsꢀwithꢀrespectꢀtoꢀλexꢀ(Fig-
ureꢀS4)ꢀindicateꢀthatꢀemissionꢀfromꢀtheꢀmixedꢀfluorophoreꢀ
systemsꢀareꢀexcitationꢀwavelengthꢀindependent.ꢀTheꢀaddi-
tiveꢀ natureꢀ ofꢀ theꢀ emissionꢀ profilesꢀ andꢀ theꢀ wavelengthꢀ
independentꢀ CIEꢀ chromaticityꢀ coordinatesꢀ areꢀ consistentꢀ
withꢀminimalꢀenergyꢀtransferꢀinꢀtheꢀyꢀ=ꢀ0.01ꢀMOFs.ꢀConse-
quently,ꢀselectiveꢀcolorꢀgenerationꢀalongꢀtheseꢀaxesꢀcouldꢀ
beꢀachievedꢀbyꢀtuningꢀtheꢀfluorophoreꢀratio.ꢀ
Forꢀ theꢀ Zr
6
O
4
4
(OH) [(R0.33
G
B
0.33 0.33
)
0.10NF0.90] ꢀ MOFꢀ (Figureꢀ
6
S7ꢀandꢀTableꢀS3),ꢀexcitedꢀstateꢀlifetimesꢀforꢀBꢀ(τ460ꢀnmꢀ=ꢀ1.5ꢀ
ns),ꢀGꢀ(τ560ꢀnmꢀ=ꢀ1.8ꢀns),ꢀandꢀRꢀ(τ660ꢀnmꢀ=ꢀ1.9ꢀns)ꢀwereꢀsimilarꢀ
toꢀthatꢀofꢀ10%-Rꢀ(τ660ꢀnmꢀ=ꢀ1.5ꢀns)ꢀbutꢀnotablyꢀshorterꢀthanꢀ
forꢀ10%-Gꢀ(τ560ꢀnmꢀ=ꢀ3.1ꢀns)ꢀandꢀ10%-Bꢀ(τ460ꢀ nmꢀ=ꢀ5.7ꢀns).ꢀ
Theꢀsimilarityꢀinꢀlifetimesꢀofꢀtheꢀthreeꢀpeaksꢀisꢀsymptomat-
icꢀ ofꢀ anꢀ energyꢀtransferꢀequilibriumꢀ conditionꢀ whereꢀ theꢀ
collectiveꢀemissionꢀdecayꢀkineticsꢀareꢀdictatedꢀbyꢀtheꢀemit-
26
terꢀwithꢀtheꢀfastestꢀradiativeꢀdecayꢀrateꢀ(i.e.,ꢀR). ꢀThatꢀis,ꢀBꢀ
energyꢀtransferꢀtoꢀRꢀandꢀG,ꢀGꢀenolꢀenergyꢀtransferꢀtoꢀRꢀandꢀ
B,ꢀ andꢀ Rꢀ enolꢀ energyꢀ transferꢀ toꢀ Gꢀ andꢀ B,ꢀ withꢀ allꢀ theseꢀ
processesꢀoccurringꢀinꢀparallel.ꢀInꢀcontrast,ꢀanꢀoverallꢀfluo-
ꢀ
rescentꢀ
Zr (OH)
.9,ꢀ2.6,ꢀandꢀ1.6ꢀnsꢀforꢀB,ꢀG,ꢀandꢀR,ꢀrespectively,ꢀmoreꢀclose-
linkꢀ
dilutionꢀ
toꢀ
1.0ꢀ
mol%,ꢀ
6
O
4
4
(R0.33
G
0.33
B
0.33
)
0.01NF0.99,ꢀresultedꢀ inꢀ lifetimesꢀ ofꢀ
3
lyꢀresembleꢀtheꢀsingleꢀcomponentꢀsystemsꢀwithꢀnoꢀenergyꢀ
transfer.ꢀꢀꢀ
Theꢀexcitation-emissionꢀmapsꢀ(FigureꢀS5)ꢀshowꢀaꢀdecreaseꢀ
inꢀexcitationꢀwavelengthꢀdependence,ꢀasꢀseenꢀinꢀotherꢀdi-
luteꢀsamples.ꢀAtꢀtheseꢀlowerꢀconcentrationsꢀanꢀincreaseꢀinꢀ
theꢀenolꢀemissionꢀisꢀobserved,ꢀmostꢀstronglyꢀforꢀR,ꢀ whichꢀ
resultsꢀinꢀdeviationsꢀfromꢀtheꢀlinearꢀtrendꢀinꢀtheꢀCIEꢀchro-
ACS Paragon Plus Environment

Page 5 of 9
Journal of the American Chemical Society
maticityꢀcoordinatesꢀ(pointsꢀLꢀandꢀM,ꢀFigureꢀ5).ꢀOnceꢀtheꢀ
concentrationꢀ ofꢀ Rꢀ isꢀ sufficientlyꢀ increasedꢀ
(Zr (OH) 0.01NF0.99)ꢀ theꢀ lowꢀ energyꢀ ketoꢀ
emissionꢀ becomesꢀ predominantꢀ (Figureꢀ 5,ꢀ pointꢀ N).ꢀ Thisꢀ
sampleꢀ exhibitsꢀ theꢀ combinedꢀ broadbandꢀ emissionꢀ fromꢀ
RGB,ꢀwithꢀCIEꢀchromaticityꢀcoordinatesꢀcloseꢀtoꢀtheꢀcenterꢀ
ofꢀ theꢀ whiteꢀlightꢀregionꢀ (0.31,ꢀ 0.33),ꢀ aꢀ quantumꢀ yieldꢀ ofꢀ
=ꢀ365ꢀnm,ꢀandꢀ(bottomꢀright)ꢀCIEꢀchromaticityꢀcoordinatesꢀ
ofꢀeachꢀsample.ꢀ
1
2
3
4
5
6
7
8
9
O
6 4
4
(R0.4
G
0.2
0.4
B )
AllꢀtheꢀMOFsꢀsynthesizedꢀareꢀporous,ꢀstableꢀtoꢀwater,ꢀhu-
midity,ꢀandꢀupꢀtoꢀ400ꢀºCꢀ(FigureꢀS91),ꢀandꢀalsoꢀcompletelyꢀ
composedꢀofꢀearth-abundantꢀelements.ꢀForꢀexample,ꢀ10%-
Bꢀ andꢀ Zr
6
O
4
(OH)
4
[(R0.33G
0.33
B
0.33
)0.01NF0.99
]
6
ꢀ haveꢀ Brunau-
4.3%,ꢀandꢀaꢀcorrelatingꢀblack-bodyꢀtemperatureꢀofꢀ6480ꢀK.ꢀ
er–Emmett–Tellerꢀ(BET)ꢀsurfaceꢀareasꢀofꢀSBETꢀ=ꢀ1620ꢀandꢀ
2
-1
Thisꢀtemperatureꢀisꢀnearlyꢀidenticalꢀtoꢀthatꢀofꢀnaturalꢀday-
1600ꢀ m ꢀ g ꢀ respectivelyꢀ (Tableꢀ S6).ꢀ Waterꢀ stabilityꢀ inꢀ
10%-Bꢀ wasꢀ demonstratedꢀ byꢀ followingꢀ changesꢀ inꢀ theꢀ
diffractionꢀpatternꢀ(FigureꢀS56)ꢀandꢀBETꢀsurfaceꢀareaꢀbe-
foreꢀandꢀafterꢀexposureꢀtoꢀwaterꢀ(FigureꢀS56-57ꢀandꢀTableꢀ
S6).ꢀ Furthermore,ꢀ theꢀ long-shelfꢀ lifeꢀ ofꢀtheꢀ materialsꢀwasꢀ
demonstratedꢀ byꢀtheꢀ lackꢀ ofꢀchangesꢀ inꢀ theirꢀ PXRDꢀevenꢀ
afterꢀ 10ꢀ monthsꢀ ofꢀ storageꢀ underꢀ laboratoryꢀ conditionsꢀ
(FigureꢀS58ꢀforꢀ10%-B).ꢀꢀ
2
7
lightꢀ(6500ꢀK) ꢀandꢀcanꢀbeꢀadjustedꢀbasedꢀonꢀtheꢀfluoro-
phoreꢀconcentrationꢀ orꢀ theꢀ ratioꢀ ofꢀ theꢀ fluorescentꢀ links.ꢀ
Byꢀincreasingꢀtheꢀoverallꢀconcentrationꢀofꢀtheꢀfluorophoresꢀ
toꢀ 10%ꢀ aꢀ warmerꢀ whiteꢀ lightꢀ canꢀ beꢀ achievedꢀ inꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
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5
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5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
Zr
6
O
4
(OH)
4
[(R0.40
G
0.20
B
0.40
)
0.10NF0.90] ꢀ whichꢀ hasꢀ CIEꢀ chro-
6
maticityꢀ coordinatesꢀ ofꢀ (0.43,ꢀ 0.39)ꢀ andꢀ aꢀ correspondingꢀ
temperatureꢀofꢀ3060ꢀK.ꢀAdditionally,ꢀutilizingꢀaꢀtwoꢀcom-
ponentꢀsystem,ꢀtakingꢀadvantageꢀofꢀtheꢀlowꢀconcentrationꢀ
enolꢀemissionꢀfromꢀR,ꢀcoolꢀwhiteꢀlightꢀcanꢀbeꢀachievedꢀinꢀ
Otherꢀmethodsꢀutilizingꢀmetal-organicꢀmaterialsꢀforꢀprepa-
rationꢀofꢀsolid-stateꢀemissionꢀoftenꢀbringꢀsignificantꢀdraw-
Zr
6
O
4
(OH)
4
[(R0.5
G
0.5
)
0.01NF0.99] ꢀ withꢀ CIEꢀ chromaticityꢀ co-
6
backs.ꢀForꢀinstance,ꢀCu I ꢀisꢀaꢀclusterꢀusedꢀtoꢀcreateꢀemis-
4
4
ordinatesꢀofꢀ(0.29,ꢀ0.33)ꢀandꢀaꢀcorrespondingꢀtemperatureꢀ
ofꢀ7820ꢀKꢀ(Figureꢀ S9).ꢀToꢀ ourꢀ knowledge,ꢀthisꢀ isꢀtheꢀ firstꢀ
exampleꢀ ofꢀ crystallineꢀ bulkꢀ materialsꢀ whoseꢀ fluorescentꢀ
propertiesꢀwereꢀadjustedꢀfollowingꢀtheꢀdilutionꢀstrategiesꢀ
usedꢀinꢀliquidꢀphaseꢀfluorescence.ꢀꢀ
siveꢀmaterials,ꢀwhichꢀhasꢀbecomeꢀaꢀgrowingꢀfieldꢀinꢀrecentꢀ
years.ꢀ Theseꢀ materialsꢀ offerꢀ similarꢀ quantumꢀ yieldsꢀ forꢀ
3
0-31
pureꢀ colors,ꢀ ca.ꢀ 9%,
ꢀ butꢀ crystalizeꢀ inꢀ lowꢀ symmetry,ꢀ
ꢀclusterꢀisꢀlessꢀridgedꢀ
unpredictableꢀspaceꢀgroups.ꢀTheꢀCu
I
4 4
comparedꢀtoꢀtheꢀzirconiumꢀcluster,ꢀwhichꢀresultsꢀinꢀclusterꢀ
deformationꢀwhenꢀdifferentꢀligandsꢀareꢀboundꢀcreatingꢀlowꢀ
AsꢀaꢀcomplimentꢀtoꢀtheꢀCIEꢀcoordinates,ꢀtheꢀcolorꢀrender-
ingꢀ indexꢀ (CRI)ꢀ isꢀ aꢀ criticalꢀ parameterꢀ inꢀ describingꢀ howꢀ
faithfullyꢀaꢀlightꢀsourceꢀrepresentsꢀtheꢀtrueꢀcolorꢀofꢀanꢀob-
jectꢀwithꢀaꢀscoreꢀofꢀ100ꢀbeingꢀaꢀsourceꢀidenticalꢀtoꢀstand-
32-33
symmetryꢀ complexꢀ crystalꢀ systems.
ꢀ Otherꢀ emissiveꢀ
materialsꢀincludeꢀMOFsꢀwhereꢀallꢀtheꢀorganicꢀlinksꢀinꢀtheꢀ
3
4
frameworkꢀ areꢀ emissiveꢀ fluorophores. ꢀ Thisꢀ resultsꢀ inꢀ
unpredictableꢀandꢀinefficientꢀfluorescenceꢀdueꢀtoꢀhighꢀin-
nerꢀfilteringꢀeffectsꢀpresentꢀinꢀtheꢀmaterial.ꢀImpregnatingꢀ
MOFsꢀwithꢀfluorescentꢀguestꢀdyesꢀcanꢀproduceꢀmulticolorꢀ
2
8
ardizedꢀdaylight. ꢀTheꢀCRIꢀvaluesꢀforꢀtheꢀaboveꢀwhiteꢀlightꢀ
MOFsꢀwereꢀcalculatedꢀandꢀtheꢀresultsꢀareꢀreportedꢀinꢀTableꢀ
S4.ꢀ
Zr
andꢀ theꢀ twoꢀ componentꢀ R/Gꢀ systemꢀ withꢀ formulaꢀ
Zr (OH) 0.01NF0.99ꢀ hadꢀaꢀCRIꢀ ofꢀ 95.ꢀForꢀcontext,ꢀ
typicalꢀ fluorescentꢀ bulbsꢀ areꢀ aroundꢀ 50ꢀ andꢀ whiteꢀ LEDsꢀ
Remarkably,ꢀ
sampleꢀ
Nꢀ
withꢀ
formulaꢀ
19
6
O
4
(OH)
4
(R0.4
G
0.2
B
0.4
)0.01NF0.99ꢀdemonstratedꢀaꢀCRIꢀ ofꢀ 93ꢀ
emission; ꢀ however,ꢀ guestꢀ diffusionꢀ raisesꢀ questionsꢀ ofꢀ
homogeneityꢀandꢀlong-termꢀstabilityꢀofꢀtheꢀmaterials.ꢀOth-
erꢀ MOF-basedꢀ emissiveꢀ materialsꢀ utilizeꢀ expensiveꢀ rare-
6
O
4
4
(R0.5
0.5
G )
earthꢀelementsꢀtoꢀachieveꢀgreenꢀandꢀredꢀfluorescence,ꢀwithꢀ
quantumꢀ yieldsꢀ rangingꢀ fromꢀ 2-50%;35-37ꢀ yet,ꢀ rare-earthꢀ
2
9
oftenꢀ scoreꢀ >80. ꢀ Theseꢀ resultsꢀ indicateꢀ thatꢀ theꢀ mixedꢀ
emitterꢀMOFsꢀareꢀcapableꢀofꢀbothꢀtunableꢀemissionꢀchro-
maticity,ꢀasꢀwellꢀasꢀaccurateꢀcolorꢀrendition.ꢀꢀ
elementsꢀ areꢀ unsustainable,ꢀ limitingꢀ theirꢀ useꢀ asꢀ appliedꢀ
38
materialsꢀinꢀtheꢀlongꢀterm. ꢀꢀAsꢀsuch,ꢀtheꢀMOFsꢀandꢀmeth-
odologyꢀpresentedꢀhereinꢀoffer:ꢀanꢀeaseꢀofꢀcharacterizationꢀ
dueꢀ toꢀtheꢀ highꢀ symmetryꢀcrystalꢀ system,ꢀtunableꢀ fluoro-
phoreꢀ concentrationꢀ toꢀ achieveꢀ higherꢀ quantumꢀ yieldsꢀ
withꢀ lessꢀ innerꢀ filtering,ꢀ andꢀ usingꢀ earthꢀ abundantꢀ ele-
ments.ꢀ
Conclusionsꢀ
Applyingꢀ theꢀ conceptꢀ ofꢀ SSSꢀ toꢀ organic-basedꢀ materialsꢀ
wasꢀaccomplishedꢀusingꢀhighꢀsymmetryꢀMOFsꢀasꢀmatrices.ꢀ
Thisꢀapproachꢀallowsꢀforꢀcircumventionꢀofꢀcommonꢀchal-
lengesꢀassociatedꢀwithꢀemissiveꢀMOFsꢀ including:ꢀ highꢀ in-
nerꢀ filteringꢀ effectsꢀ thatꢀ causeꢀ complexꢀ emission,ꢀ dueꢀ toꢀ
highꢀ fluorophoreꢀ concentration,ꢀ andꢀ highꢀ syntheticꢀ costsꢀ
dueꢀtoꢀinclusionꢀofꢀlanthanides.ꢀThisꢀapproachꢀwillꢀfurtherꢀ
enableꢀtheꢀabilityꢀtoꢀstudyꢀotherꢀsimilarꢀorganic-basedꢀmo-
lecularꢀ phenomenaꢀ inꢀ solids,ꢀ andꢀ canꢀ provideꢀ organic-
basedꢀSSSꢀmaterialsꢀforꢀhighꢀprecisionꢀapplicationsꢀsuchꢀasꢀ
inꢀphotonicꢀdevices,ꢀandꢀhigh-definitionꢀdisplays.ꢀꢀ
Figureꢀ5ꢀThreeꢀcomponentꢀSSSꢀMOFs:ꢀ(Top)ꢀOpticalꢀimag-
esꢀofꢀsamplesꢀunderꢀλexꢀ=ꢀ365ꢀnmꢀindicatingꢀtheirꢀfluoro-
ASSOCIATED CONTENT
SupportingꢀInformation.ꢀMaterialsꢀandꢀmethods,ꢀfullꢀmateri-
alsꢀandꢀphotophysicalꢀcharacterization,ꢀsingleꢀcrystalꢀcrystal-
phoreꢀcomposition,ꢀ(bottomꢀleft)ꢀemissionꢀprofilesꢀwithꢀλex
ꢀ
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lographicꢀ informationꢀ file.ꢀ Thisꢀ materialꢀ isꢀ availableꢀ freeꢀ ofꢀ
chargeꢀviaꢀtheꢀInternetꢀatꢀhttp://pubs.acs.org.ꢀ
13. Lippke, J.; Brosent, B.; von Zons, T.; Virmani, E.; Lilienthal,
S.; Preuße, T.; Hülsmann, M.; Schneider, A. M.; Wuttke, S.;
Behrens, P.; Godt, A., Expanding the group of porous
interpenetrated Zr-organic frameworks (PIZOFs) with linkers of
different lengths. Inorganic Chemistry 2017, 56 (2), 748-761.
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AUTHOR INFORMATION
Corresponding Author
14. Nayak, M. K., Synthesis, characterization and optical
properties of aryl and diaryl substituted phenanthroimidazoles.
Journal of Photochemistry and Photobiology A: Chemistry 2012,
241, 26-37.
15. Park, S.; Kwon, J. E.; Park, S. Y., Strategic emission color
tuning of highly fluorescent imidazole-based excited-state
intramolecular proton transfer molecules. Physical Chemistry
Chemical Physics 2012, 14 (25), 8878-8884.
16. Kwon, J. E.; Park, S.; Park, S. Y., Realizing molecular pixel
system for full-color fluorescence reproduction: RGB-emitting
molecular mixture free from energy transfer crosstalk. Journal of
the American Chemical Society 2013, 135 (30), 11239-11246.
fernando@ucf.edu,ꢀandꢀhanson@chem.fsu.eduꢀꢀ
Author Contributions
Theꢀmanuscriptꢀwasꢀwrittenꢀthroughꢀcontributionsꢀofꢀallꢀau-
thors.ꢀAllꢀauthorsꢀhaveꢀgivenꢀapprovalꢀtoꢀtheꢀfinalꢀversionꢀofꢀ
theꢀmanuscript.ꢀꢀ
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Funding Sources
Synthesisꢀofꢀmaterialsꢀ(CHE-1665257,ꢀFJU-R)ꢀandꢀPhotophysi-
calꢀmeasurementsꢀ(CHE-1531629,ꢀKH)ꢀwereꢀsupportedꢀbyꢀtheꢀ
NationalꢀScienceꢀFoundation.ꢀ
ꢀ
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7. Kwon, J. E.; Park, S. Y., Advanced organic optoelectronic
materials: harnessing excited-state intramolecular proton transfer
ESIPT) process. Advanced Materials 2011, 23 (32), 3615-3642.
8. Han, S.; Wei, Y.; Valente, C.; Lagzi, I.; Gassensmith, J. J.;
(
1
ACKNOWLEDGMENTS
Coskun, A.; Stoddart, J. F.; Grzybowski, B. A., Chromatography
in a single metal−organic framework (MOF) crystal. Journal of
the American Chemical Society 2010, 132 (46), 16358-16361.
19. Ullman, A. M.; Brown, J. W.; Foster, M. E.; Léonard, F.;
Leong, K.; Stavila, V.; Allendorf, M. D., Transforming MOFs for
Energy Applications Using the Guest@MOF Concept. Inorganic
Chemistry 2016, 55 (15), 7233-7249.
Weꢀ wouldꢀ likeꢀ toꢀ thankꢀ Dr.ꢀ Markꢀ Maricꢀ (UCF)ꢀ forꢀ technicalꢀ
assistanceꢀandꢀDr.ꢀTitelꢀJurcaꢀ(UCF)ꢀforꢀhelpfulꢀdiscussions.ꢀꢀ
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