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Journal of the American Chemical Society
Article . 2013 . Peer-reviewed
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Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal–Organic Frameworks

Authors: Nak Cheon Jeong; Nak Cheon Jeong; Christopher E. Wilmer; Sameer Patwardhan; Shengye Jin; Gary P. Wiederrecht; George C. Schatz; +8 Authors

Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal–Organic Frameworks

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.

Country
Korea (Republic of)
Keywords

Chlorophyll, Acetylene Derivative, Light, Java Programming Language, Light-Harvesting System, Ultra-Fast Energy Migration, Fluorescence Quenching, Energy Migration, Pentafluorophenyl, Light-Harvesting, [5,15 Dipyridyl 10,20 Bis(Pentafluorophenyl)Porphinato]Zinc (ii), Pyridyl, Photosynthesis, Struts, Molecular Structure, Acetylene, Theoretical Calculations, Calculation, Metal Organic Framework, Zinc, Photogenerated Excitons, Excitons, High Anisotropy, [5,15 Bis[4 (Pyridyl)Ethynyl] 10,20 Diphenylporphinato]Zinc (ii), Crystalline Materials, Ethynyl, Porphyrins, Metalloporphyrins, Ultra-Fast, Fluorescence, Absorption, Absorption Intensity, Porphyrin, Unclassified Drug, Energy-Transport, Solar Energy, Organometallic Compounds, Harvesting, Controlled Study, Energy Conversion, Conjugation, Theoretical Model, 500, 540, Energy Transfer, Antenna, Zinc Compounds, Exciton Migration, Related Compounds, Anisotropy, Addition Reaction, Porphyrin Molecules

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    534
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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
534
Top 0.1%
Top 1%
Top 0.1%
bronze