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Title: Toward Metal–Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures

Abstract

Owing to their ability to act as light-harvesting scaffolds, porphyrin-containing metal-organic frameworks (MOFs) are in the forefront of research on the application of highly ordered molecular materials to problems in solar-energy conversion. In this work, solvent-assisted linker exchange (SALE) is performed on a pillared paddlewheel porphyrin containing MOF thin film to collapse a 3D framework to a 2D framework. The change in dimensionality of the framework is confirmed by a decrease in the film thickness, the magnitude of which is in agreement with crystallographic parameters for related bulk materials. Furthermore, NMR spectroscopy performed on the digested sample suggests a similar change in geometry is achieved in bulk MOF samples. The decreased distance between the porphyrin chromophores in the 2D MOF film compared to the 3D film results in enhanced energy transfer through the film. The extent of energy transport was probed by assembling MOF thin film where the outermost layers are palladium porphyrin (P2) units, which act as energy traps and fluorescence quenchers. Steady-state emission spectroscopy together with time-resolved emission spectroscopy indicates that excitons can travel through about 9-11 layers (porphyrin layers) in 2D films, whereas in 3D films energy transfer occurs through no more than about 6-8 layers. Themore » results are difficult to understand if only changes in MOF interlayer spacing are considered but become much more understandable if dipole-dipole coupling distances are considered.« less

Authors:
; ; ; ; ;
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:
1352583
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 8; Journal Issue: 45; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Goswami, Subhadip, Ma, Lin, Martinson, Alex B. F., Wasielewski, Michael R., Farha, Omar K., and Hupp, Joseph T. Toward Metal–Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures. United States: N. p., 2016. Web. doi:10.1021/acsami.6b08552.
Goswami, Subhadip, Ma, Lin, Martinson, Alex B. F., Wasielewski, Michael R., Farha, Omar K., & Hupp, Joseph T. Toward Metal–Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures. United States. https://doi.org/10.1021/acsami.6b08552
Goswami, Subhadip, Ma, Lin, Martinson, Alex B. F., Wasielewski, Michael R., Farha, Omar K., and Hupp, Joseph T. Wed . "Toward Metal–Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures". United States. https://doi.org/10.1021/acsami.6b08552.
@article{osti_1352583,
title = {Toward Metal–Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures},
author = {Goswami, Subhadip and Ma, Lin and Martinson, Alex B. F. and Wasielewski, Michael R. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Owing to their ability to act as light-harvesting scaffolds, porphyrin-containing metal-organic frameworks (MOFs) are in the forefront of research on the application of highly ordered molecular materials to problems in solar-energy conversion. In this work, solvent-assisted linker exchange (SALE) is performed on a pillared paddlewheel porphyrin containing MOF thin film to collapse a 3D framework to a 2D framework. The change in dimensionality of the framework is confirmed by a decrease in the film thickness, the magnitude of which is in agreement with crystallographic parameters for related bulk materials. Furthermore, NMR spectroscopy performed on the digested sample suggests a similar change in geometry is achieved in bulk MOF samples. The decreased distance between the porphyrin chromophores in the 2D MOF film compared to the 3D film results in enhanced energy transfer through the film. The extent of energy transport was probed by assembling MOF thin film where the outermost layers are palladium porphyrin (P2) units, which act as energy traps and fluorescence quenchers. Steady-state emission spectroscopy together with time-resolved emission spectroscopy indicates that excitons can travel through about 9-11 layers (porphyrin layers) in 2D films, whereas in 3D films energy transfer occurs through no more than about 6-8 layers. The results are difficult to understand if only changes in MOF interlayer spacing are considered but become much more understandable if dipole-dipole coupling distances are considered.},
doi = {10.1021/acsami.6b08552},
url = {https://www.osti.gov/biblio/1352583}, journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 45,
volume = 8,
place = {United States},
year = {2016},
month = {11}
}