J-dimer emission in interwoven metal-organic frameworks

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dc.contributor.authorNewsome, Wesley J.en
dc.contributor.authorChakraborty, Arnaben
dc.contributor.authorLy, Richard T.en
dc.contributor.authorPour, Gavin S.en
dc.contributor.authorFairchild, David C.en
dc.contributor.authorMorris, Amanda J.en
dc.contributor.authorUribe-Romo, Fernando J.en
dc.contributor.departmentChemistryen
dc.date.accessioned2020-08-18T13:57:54Zen
dc.date.available2020-08-18T13:57:54Zen
dc.date.issued2020-05-07en
dc.description.abstractJ-dimer emission is an emergent property that occurs when pairs of ground state fluorophores associate, typically in a dilute solution medium. The resulting fluorescence is shifted with respect to the monomer. J-dimer emission, however, has never been observed in concentrated dispersions or in the solid state. We posited that multivariate (MTV) MOFs with double interwoven structures would help to isolate these dimers within their crystalline matrix. Using this strategy, J-aggregate density was controlled during crystallization by following a substitutional solid solution approach. Here, we identified the presence of J-dimers over the entire composition range for interwoven PIZOF-2/NNU-28 structures with variable amounts of a diethynyl-anthracene aggregate-forming link. We produced bulk crystals that systematically shifted their fluorescence from green to red with lifetimes (up to 13 ns) and quantum yields (up to 76%) characteristic of pi-pi stacked aggregates. Photophysical studies also revealed an equilibrium constant of dimerization, K-D = 1.5 +/- 0.3 M-1, enabling the first thermodynamic quantification of link-link interactions that occur during MOF assembly. Our findings elucidate the role that supramolecular effects play during crystallization of MTV MOFs, opening pathways for the preparation of solid-state materials with solution-like properties by design.en
dc.description.notesF. Uribe-Romo would like to acknowledge that this material was supported by the National Science Foundation (CHE-1665277). A. Morris would like to acknowledge that this material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0012446.en
dc.description.sponsorshipNational Science FoundationNational Science Foundation (NSF) [CHE-1665277]; U.S. Department of Energy, Office of Science, Office of Basic Energy SciencesUnited States Department of Energy (DOE) [DE-SC0012446]en
dc.format.mimetypeapplication/pdfen
dc.identifier.doihttps://doi.org/10.1039/d0sc00876aen
dc.identifier.eissn2041-6539en
dc.identifier.issn2041-6520en
dc.identifier.issue17en
dc.identifier.urihttp://hdl.handle.net/10919/99732en
dc.identifier.volume11en
dc.language.isoenen
dc.rightsCreative Commons Attribution-NonCommercial 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by-nc/4.0/en
dc.titleJ-dimer emission in interwoven metal-organic frameworksen
dc.title.serialChemical Scienceen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten
dc.type.dcmitypeStillImageen

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