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Title: Boosting Transport Distances for Molecular Excitons within Photoexcited Metal–Organic Framework Films

Abstract

In this paper, we describe the fabrication of porphyrin-containing metal-organic framework thin films with 1,4-diazabicyclo[2.2.2]octane (DABCO) pillaring linkers and investigate exciton transport within the films. Steady-state emission spectroscopy indicates that the exciton can traverse up to 26 porphyrin layers when DABCO is used as a pillaring linker, whereas on average only 9-11 layers can be traversed when either 4,4'-bipyridine (a pillaring linker) or pyridine (a nonpillaring, layer-interdigitating ligand) is used. These results can be understood by taking into account the decreased separation distances between transition dipoles associated with chromophores (porphyrins) sited in adjacent layers. Shorter distances translate into faster Forster-type exciton hopping and, therefore, more hops within the few nanosecond lifetime of the porphyrin's singlet excited-state. Lastly, the findings have favorable implications for the development of MOF-based photoelectrodes and photoelectrochemical energy-conversion devices.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)
  3. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1487133
Grant/Contract Number:  
AC02-06CH11357; FG02-87ER13808; FG02-99ER14999
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 40; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; energy transfer; exciton hopping; layer-by-layer; metal−organic framework; transition dipole

Citation Formats

Goswami, Subhadip, Chen, Michelle, Wasielewski, Michael R., Farha, Omar K., and Hupp, Joseph T. Boosting Transport Distances for Molecular Excitons within Photoexcited Metal–Organic Framework Films. United States: N. p., 2018. Web. doi:10.1021/acsami.8b14977.
Goswami, Subhadip, Chen, Michelle, Wasielewski, Michael R., Farha, Omar K., & Hupp, Joseph T. Boosting Transport Distances for Molecular Excitons within Photoexcited Metal–Organic Framework Films. United States. doi:10.1021/acsami.8b14977.
Goswami, Subhadip, Chen, Michelle, Wasielewski, Michael R., Farha, Omar K., and Hupp, Joseph T. Wed . "Boosting Transport Distances for Molecular Excitons within Photoexcited Metal–Organic Framework Films". United States. doi:10.1021/acsami.8b14977. https://www.osti.gov/servlets/purl/1487133.
@article{osti_1487133,
title = {Boosting Transport Distances for Molecular Excitons within Photoexcited Metal–Organic Framework Films},
author = {Goswami, Subhadip and Chen, Michelle and Wasielewski, Michael R. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {In this paper, we describe the fabrication of porphyrin-containing metal-organic framework thin films with 1,4-diazabicyclo[2.2.2]octane (DABCO) pillaring linkers and investigate exciton transport within the films. Steady-state emission spectroscopy indicates that the exciton can traverse up to 26 porphyrin layers when DABCO is used as a pillaring linker, whereas on average only 9-11 layers can be traversed when either 4,4'-bipyridine (a pillaring linker) or pyridine (a nonpillaring, layer-interdigitating ligand) is used. These results can be understood by taking into account the decreased separation distances between transition dipoles associated with chromophores (porphyrins) sited in adjacent layers. Shorter distances translate into faster Forster-type exciton hopping and, therefore, more hops within the few nanosecond lifetime of the porphyrin's singlet excited-state. Lastly, the findings have favorable implications for the development of MOF-based photoelectrodes and photoelectrochemical energy-conversion devices.},
doi = {10.1021/acsami.8b14977},
journal = {ACS Applied Materials and Interfaces},
number = 40,
volume = 10,
place = {United States},
year = {2018},
month = {9}
}

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