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

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [1];  [1];  [2];  [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)
+ Show Author Affiliations
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.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357; FG02-87ER13808; FG02-99ER14999
OSTI ID:
1487133
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 40 Vol. 10; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
energy transfer
exciton hopping
layer-by-layer
metal−organic framework
transition dipole