Mapping Forbidden Emission to Structure in Self-Assembled Organic Nanoparticles

Daniel A. Hinton, James D. Ng, Jian Sun, Stephen Lee, Semion K. Saikin, Jenna Logsdon, David S. White, Angela N. Marquard, Andrew C. Cavell, Veronica K. Krasecki, Kassandra A. Knapper, Katherine M. Lupo, Michael R Wasielewski, Alán Aspuru-Guzik, Julie S. Biteen, Padma Gopalan, Randall H. Goldsmith

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The interplay between micromorphology and electronic properties is an important theme in organic electronic materials. Here, we show that a spirofluorene-functionalized boron-dipyrromethene (BODIPY) with an alkyl norbornyl tail self-assembles into nanoparticles with qualitatively different properties as compared to the polymerized species. Further, the nanoparticles exhibit a host of unique emissive properties, including photobrightening, a blue satellite peak, and spectral diffusion. Extensive photophysical characterization, including single-particle imaging and spectroscopy, and time-resolved fluorescence, coupled with electronic structure calculations based on an experimentally determined crystal structure, allow a mechanism to be developed. Specifically, BODIPY chromophores are observed to form quasi-two-dimensional layers, where stacking of unit cells adds either J-aggregate character or H-aggregate character depending on the direction of the stacking. Particularly strongly H-coupled domains show the rare process of emission from an upper exciton state, in violation of Kasha's rule, and result in the blue satellite peak. The spatial heterogeneity of structure thus maps onto a gradient of photophysical behavior as seen in single-particle imaging, and the temporal evolution of structure maps onto fluctuating emissive behavior, as seen in single-particle spectroscopy. Taken together, this system provides a striking example of how physical structure and electronic properties are intertwined, and a rare opportunity to use one to chart the other.

Original languageEnglish
Pages (from-to)15827-15841
Number of pages15
JournalJournal of the American Chemical Society
Volume140
Issue number46
DOIs
Publication statusPublished - Nov 21 2018

Fingerprint

Boron
Electronic properties
Nanoparticles
Spectrum Analysis
Satellites
Spectroscopy
Imaging techniques
Chromophores
Excitons
Electronic structure
Crystal structure
Fluorescence
dipyrromethene
LDS 751
Direction compound

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hinton, D. A., Ng, J. D., Sun, J., Lee, S., Saikin, S. K., Logsdon, J., ... Goldsmith, R. H. (2018). Mapping Forbidden Emission to Structure in Self-Assembled Organic Nanoparticles. Journal of the American Chemical Society, 140(46), 15827-15841. https://doi.org/10.1021/jacs.8b09149

Mapping Forbidden Emission to Structure in Self-Assembled Organic Nanoparticles. / Hinton, Daniel A.; Ng, James D.; Sun, Jian; Lee, Stephen; Saikin, Semion K.; Logsdon, Jenna; White, David S.; Marquard, Angela N.; Cavell, Andrew C.; Krasecki, Veronica K.; Knapper, Kassandra A.; Lupo, Katherine M.; Wasielewski, Michael R; Aspuru-Guzik, Alán; Biteen, Julie S.; Gopalan, Padma; Goldsmith, Randall H.

In: Journal of the American Chemical Society, Vol. 140, No. 46, 21.11.2018, p. 15827-15841.

Research output: Contribution to journalArticle

Hinton, DA, Ng, JD, Sun, J, Lee, S, Saikin, SK, Logsdon, J, White, DS, Marquard, AN, Cavell, AC, Krasecki, VK, Knapper, KA, Lupo, KM, Wasielewski, MR, Aspuru-Guzik, A, Biteen, JS, Gopalan, P & Goldsmith, RH 2018, 'Mapping Forbidden Emission to Structure in Self-Assembled Organic Nanoparticles', Journal of the American Chemical Society, vol. 140, no. 46, pp. 15827-15841. https://doi.org/10.1021/jacs.8b09149
Hinton, Daniel A. ; Ng, James D. ; Sun, Jian ; Lee, Stephen ; Saikin, Semion K. ; Logsdon, Jenna ; White, David S. ; Marquard, Angela N. ; Cavell, Andrew C. ; Krasecki, Veronica K. ; Knapper, Kassandra A. ; Lupo, Katherine M. ; Wasielewski, Michael R ; Aspuru-Guzik, Alán ; Biteen, Julie S. ; Gopalan, Padma ; Goldsmith, Randall H. / Mapping Forbidden Emission to Structure in Self-Assembled Organic Nanoparticles. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 46. pp. 15827-15841.
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