Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks

Ho Jin Son, Shengye Jin, Sameer Patwardhan, Sander J. Wezenberg, Nak Cheon Jeong, Monica So, Christopher E. Wilmer, Amy A. Sarjeant, George C Schatz, Randall Q. Snurr, Omar K. Farha, Gary P. Wiederrecht, Joseph T Hupp

Research output: Contribution to journalArticle

305 Citations (Scopus)

Abstract

Given that energy (exciton) migration in natural photosynthesis primarily occurs in highly ordered porphyrin-like pigments (chlorophylls), equally highly ordered porphyrin-based metal-organic frameworks (MOFs) might be expected to exhibit similar behavior, thereby facilitating antenna-like light-harvesting and positioning such materials for use in solar energy conversion schemes. Herein, we report the first example of directional, long-distance energy migration within a MOF. Two MOFs, namely F-MOF and DA-MOF that are composed of two Zn(II) porphyrin struts [5,15-dipyridyl-10,20-bis(pentafluorophenyl)porphinato]zinc(II) and [5,15-bis[4-(pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II), respectively, were investigated. From fluorescence quenching experiments and theoretical calculations, we find that the photogenerated exciton migrates over a net distance of up to ∼45 porphyrin struts within its lifetime in DA-MOF (but only ∼3 in F-MOF), with a high anisotropy along a specific direction. The remarkably efficient exciton migration in DA-MOF is attributed to enhanced π-conjugation through the addition of two acetylene moieties in the porphyrin molecule, which leads to greater Q-band absorption intensity and much faster exciton-hopping (energy transfer between adjacent porphyrin struts). The long distance and directional energy migration in DA-MOF suggests promising applications of this compound or related compounds in solar energy conversion schemes as an efficient light-harvesting and energy-transport component.

Original languageEnglish
Pages (from-to)862-869
Number of pages8
JournalJournal of the American Chemical Society
Volume135
Issue number2
DOIs
Publication statusPublished - Jan 16 2013

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Porphyrins
Metals
Light
Excitons
Struts
Solar Energy
Energy conversion
Solar energy
Zinc
Acetylene
Photosynthesis
Energy Transfer
Anisotropy
Chlorophyll
Pigments
Energy transfer
Absorption spectra
Quenching
Fluorescence
Antennas

ASJC Scopus subject areas

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

Cite this

Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks. / Son, Ho Jin; Jin, Shengye; Patwardhan, Sameer; Wezenberg, Sander J.; Jeong, Nak Cheon; So, Monica; Wilmer, Christopher E.; Sarjeant, Amy A.; Schatz, George C; Snurr, Randall Q.; Farha, Omar K.; Wiederrecht, Gary P.; Hupp, Joseph T.

In: Journal of the American Chemical Society, Vol. 135, No. 2, 16.01.2013, p. 862-869.

Research output: Contribution to journalArticle

Son, HJ, Jin, S, Patwardhan, S, Wezenberg, SJ, Jeong, NC, So, M, Wilmer, CE, Sarjeant, AA, Schatz, GC, Snurr, RQ, Farha, OK, Wiederrecht, GP & Hupp, JT 2013, 'Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks', Journal of the American Chemical Society, vol. 135, no. 2, pp. 862-869. https://doi.org/10.1021/ja310596a
Son, Ho Jin ; Jin, Shengye ; Patwardhan, Sameer ; Wezenberg, Sander J. ; Jeong, Nak Cheon ; So, Monica ; Wilmer, Christopher E. ; Sarjeant, Amy A. ; Schatz, George C ; Snurr, Randall Q. ; Farha, Omar K. ; Wiederrecht, Gary P. ; Hupp, Joseph T. / Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 2. pp. 862-869.
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AU - So, Monica

AU - Wilmer, Christopher E.

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AU - Wiederrecht, Gary P.

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