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Title: Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping

Abstract

Metal–organic frameworks (MOFs) with light-harvesting building blocks designed to mimic photosynthetic chromophore arrays in green plants provide an excellent platform to study exciton transport in networks with well-defined structures. A step-by-step exciton random hopping model made of the elementary steps of energy transfer between only the nearest neighbors is usually used to describe the transport dynamics. Although such a nearest neighbor approximation is valid in describing the energy transfer of triplet states via the Dexter mechanism, we found it inadequate in evaluating singlet exciton migration that occurs through the Förster mechanism, which involves one-step jumping over longer distance. We measured migration rates of singlet excitons on two MOFs constructed from truxene-derived ligands and zinc nodes, by monitoring energy transfer from the MOF skeleton to a coumarin probe in the MOF cavity. The diffusivities of the excitons on the frameworks were determined to be 1.8 × 10–2 cm2/s and 2.3 × 10–2 cm2/s, corresponding to migration distances of 43 and 48 nm within their lifetimes, respectively. “Through space” energy-jumping beyond nearest neighbor accounts for up to 67% of the energy transfer rates. This finding presents a new perspective in the design and understanding of highly efficient energy transport networks for singletmore » excited states.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1];  [1];  [1];  [3]
  1. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China
  2. Department of Chemistry, University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States
  3. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China, Department of Chemistry, University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1247615
Alternate Identifier(s):
OSTI ID: 1337702
Grant/Contract Number:  
21471126; NSF/CHE-1346572; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 16; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dyes and pigments; Excitons; Energy transfer; Ligands; Metal organic frameworks

Citation Formats

Zhang, Qiongqiong, Zhang, Cankun, Cao, Lingyun, Wang, Zi, An, Bing, Lin, Zekai, Huang, Ruiyun, Zhang, Zhiming, Wang, Cheng, and Lin, Wenbin. Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping. United States: N. p., 2016. Web. doi:10.1021/jacs.6b01345.
Zhang, Qiongqiong, Zhang, Cankun, Cao, Lingyun, Wang, Zi, An, Bing, Lin, Zekai, Huang, Ruiyun, Zhang, Zhiming, Wang, Cheng, & Lin, Wenbin. Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping. United States. doi:10.1021/jacs.6b01345.
Zhang, Qiongqiong, Zhang, Cankun, Cao, Lingyun, Wang, Zi, An, Bing, Lin, Zekai, Huang, Ruiyun, Zhang, Zhiming, Wang, Cheng, and Lin, Wenbin. Mon . "Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping". United States. doi:10.1021/jacs.6b01345.
@article{osti_1247615,
title = {Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping},
author = {Zhang, Qiongqiong and Zhang, Cankun and Cao, Lingyun and Wang, Zi and An, Bing and Lin, Zekai and Huang, Ruiyun and Zhang, Zhiming and Wang, Cheng and Lin, Wenbin},
abstractNote = {Metal–organic frameworks (MOFs) with light-harvesting building blocks designed to mimic photosynthetic chromophore arrays in green plants provide an excellent platform to study exciton transport in networks with well-defined structures. A step-by-step exciton random hopping model made of the elementary steps of energy transfer between only the nearest neighbors is usually used to describe the transport dynamics. Although such a nearest neighbor approximation is valid in describing the energy transfer of triplet states via the Dexter mechanism, we found it inadequate in evaluating singlet exciton migration that occurs through the Förster mechanism, which involves one-step jumping over longer distance. We measured migration rates of singlet excitons on two MOFs constructed from truxene-derived ligands and zinc nodes, by monitoring energy transfer from the MOF skeleton to a coumarin probe in the MOF cavity. The diffusivities of the excitons on the frameworks were determined to be 1.8 × 10–2 cm2/s and 2.3 × 10–2 cm2/s, corresponding to migration distances of 43 and 48 nm within their lifetimes, respectively. “Through space” energy-jumping beyond nearest neighbor accounts for up to 67% of the energy transfer rates. This finding presents a new perspective in the design and understanding of highly efficient energy transport networks for singlet excited states.},
doi = {10.1021/jacs.6b01345},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 138,
place = {United States},
year = {2016},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1021/jacs.6b01345

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Cited by: 30 works
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Works referencing / citing this record:

van der Waals Metal-Organic Framework as an Excitonic Material for Advanced Photonics
journal, January 2017

  • Milichko, Valentin A.; Makarov, Sergey V.; Yulin, Alexey V.
  • Advanced Materials, Vol. 29, Issue 12
  • DOI: 10.1002/adma.201606034

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
journal, July 2019

  • Mezenov, Yuri A.; Krasilin, Andrei A.; Dzyuba, Vladimir P.
  • Advanced Science, Vol. 6, Issue 17
  • DOI: 10.1002/advs.201900506

Hierarchical Corannulene-Based Materials: Energy Transfer and Solid-State Photophysics
journal, March 2017

  • Rice, Allison M.; Fellows, W. Brett; Dolgopolova, Ekaterina A.
  • Angewandte Chemie International Edition, Vol. 56, Issue 16
  • DOI: 10.1002/anie.201612199

Modifying electron transfer between photoredox and organocatalytic units via framework interpenetration for β-carbonyl functionalization
journal, August 2017


Integration of a (–Cu–S–)n plane in a metal–organic framework affords high electrical conductivity
journal, April 2019


Mechanistic insight into the sensing of nitroaromatic compounds by metal-organic frameworks
journal, March 2019


The 3D [(Cu 2 Br 2 ){μ-EtS(CH 2 ) 4 SEt}] n material: a rare example of a coordination polymer exhibiting triplet–triplet annihilation
journal, January 2016

  • Bonnot, Antoine; Karsenti, Paul-Ludovic; Juvenal, Frank
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 36
  • DOI: 10.1039/c6cp04728a

A highly emissive and stable zinc( ii ) metal–organic framework as a host–guest chemopalette for approaching white-light-emission
journal, January 2017

  • Cai, Hong; Xu, Li-Li; Lai, He-Yun
  • Chemical Communications, Vol. 53, Issue 56
  • DOI: 10.1039/c7cc03350h

Unique structural micro-adjustments in a new benzothiadiazole-derived Zn( ii ) metal organic framework via simple photochemical decarboxylation
journal, January 2017

  • Han, Xiao; Cheng, Qing; Meng, Xiangru
  • Chemical Communications, Vol. 53, Issue 74
  • DOI: 10.1039/c7cc06125k

Photonic functional metal–organic frameworks
journal, January 2018

  • Cui, Yuanjing; Zhang, Jun; He, Huajun
  • Chemical Society Reviews, Vol. 47, Issue 15
  • DOI: 10.1039/c7cs00879a

Cu( i ) coordination polymers (CPs) as tandem catalysts for three-component sequential click/alkynylation cycloaddition reaction with regiocontrol
journal, January 2018

  • Guo, Xiaoqing; Huang, Chao; Yang, Haiyan
  • Dalton Transactions, Vol. 47, Issue 47
  • DOI: 10.1039/c8dt04067b

van der Waals Metal-Organic Framework as an Excitonic Material for Advanced Photonics
journal, January 2017

  • Milichko, Valentin A.; Makarov, Sergey V.; Yulin, Alexey V.
  • Advanced Materials, Vol. 29, Issue 12
  • DOI: 10.1002/adma.201606034

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
journal, July 2019

  • Mezenov, Yuri A.; Krasilin, Andrei A.; Dzyuba, Vladimir P.
  • Advanced Science, Vol. 6, Issue 17
  • DOI: 10.1002/advs.201900506

Hierarchical Corannulene-Based Materials: Energy Transfer and Solid-State Photophysics
journal, March 2017

  • Rice, Allison M.; Fellows, W. Brett; Dolgopolova, Ekaterina A.
  • Angewandte Chemie, Vol. 129, Issue 16
  • DOI: 10.1002/ange.201612199

Modifying electron transfer between photoredox and organocatalytic units via framework interpenetration for β-carbonyl functionalization
journal, August 2017


Integration of a (–Cu–S–)n plane in a metal–organic framework affords high electrical conductivity
journal, April 2019


Mechanistic insight into the sensing of nitroaromatic compounds by metal-organic frameworks
journal, March 2019


The 3D [(Cu 2 Br 2 ){μ-EtS(CH 2 ) 4 SEt}] n material: a rare example of a coordination polymer exhibiting triplet–triplet annihilation
journal, January 2016

  • Bonnot, Antoine; Karsenti, Paul-Ludovic; Juvenal, Frank
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 36
  • DOI: 10.1039/c6cp04728a

A highly emissive and stable zinc( ii ) metal–organic framework as a host–guest chemopalette for approaching white-light-emission
journal, January 2017

  • Cai, Hong; Xu, Li-Li; Lai, He-Yun
  • Chemical Communications, Vol. 53, Issue 56
  • DOI: 10.1039/c7cc03350h

Unique structural micro-adjustments in a new benzothiadiazole-derived Zn( ii ) metal organic framework via simple photochemical decarboxylation
journal, January 2017

  • Han, Xiao; Cheng, Qing; Meng, Xiangru
  • Chemical Communications, Vol. 53, Issue 74
  • DOI: 10.1039/c7cc06125k

Photonic functional metal–organic frameworks
journal, January 2018

  • Cui, Yuanjing; Zhang, Jun; He, Huajun
  • Chemical Society Reviews, Vol. 47, Issue 15
  • DOI: 10.1039/c7cs00879a

Cu( i ) coordination polymers (CPs) as tandem catalysts for three-component sequential click/alkynylation cycloaddition reaction with regiocontrol
journal, January 2018

  • Guo, Xiaoqing; Huang, Chao; Yang, Haiyan
  • Dalton Transactions, Vol. 47, Issue 47
  • DOI: 10.1039/c8dt04067b

Hierarchical Corannulene-Based Materials: Energy Transfer and Solid-State Photophysics
journal, March 2017

  • Rice, Allison M.; Fellows, W. Brett; Dolgopolova, Ekaterina A.
  • Angewandte Chemie International Edition, Vol. 56, Issue 16
  • DOI: 10.1002/anie.201612199

Trapped Photons Induced Ultrahigh External Quantum Efficiency and Photoresponsivity in Hybrid Graphene/Metal-Organic Framework Broadband Wearable Photodetectors
journal, October 2018

  • Bera, Krishna Prasad; Haider, Golam; Usman, Muhammad
  • Advanced Functional Materials, Vol. 28, Issue 51
  • DOI: 10.1002/adfm.201804802

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach
journal, November 2019

  • Haldar, Ritesh; Heinke, Lars; Wöll, Christof
  • Advanced Materials, Vol. 32, Issue 20
  • DOI: 10.1002/adma.201905227

Triindolo-Truxene Derivatives: Design, Synthesis, and Fine-Tuning of Electronic Properties and Molecular Assembly through Molecular Engineering
journal, December 2018

  • Chen, Jun-Bo; Zhou, Cen; Lu, Ru-Qiang
  • Chemistry - A European Journal, Vol. 25, Issue 5
  • DOI: 10.1002/chem.201804457

Anisotropic energy transfer in crystalline chromophore assemblies
journal, October 2018


Future and challenges for hybrid upconversion nanosystems
journal, October 2019


Enhancing the photoluminescence of surface anchored metal–organic frameworks: mixed linkers and efficient acceptors
journal, January 2018

  • Oldenburg, M.; Turshatov, A.; Busko, D.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 17
  • DOI: 10.1039/c7cp08452h

Photochemistry and photophysics of MOFs: steps towards MOF-based sensing enhancements
journal, January 2018

  • Dolgopolova, Ekaterina A.; Rice, Allison M.; Martin, Corey R.
  • Chemical Society Reviews, Vol. 47, Issue 13
  • DOI: 10.1039/c7cs00861a

A multi-dye@MOF composite boosts highly efficient photodegradation of an ultra-stubborn dye reactive blue 21 under visible-light irradiation
journal, January 2018

  • Li, Qing; Fan, Zeng-Lu; Xue, Dong-Xu
  • Journal of Materials Chemistry A, Vol. 6, Issue 5
  • DOI: 10.1039/c7ta10184h

Green applications of metal–organic frameworks
journal, January 2018

  • Ajoyan, Zvart; Marino, Paola; Howarth, Ashlee J.
  • CrystEngComm, Vol. 20, Issue 39
  • DOI: 10.1039/c8ce01002a

Light harvesting and energy transfer in a porphyrin-based metal organic framework
journal, January 2019

  • Shaikh, Shaunak M.; Chakraborty, Arnab; Alatis, James
  • Faraday Discussions, Vol. 216
  • DOI: 10.1039/c8fd00194d

Energy transfer on a two-dimensional antenna enhances the photocatalytic activity of CO 2 reduction by metal–organic layers
journal, January 2019

  • Hu, Xuefu; Chen, Peican; Zhang, Cankun
  • Chemical Communications, Vol. 55, Issue 65
  • DOI: 10.1039/c9cc04594e

Unusual triplet–triplet annihilation in a 3D copper( i ) chloride coordination polymer
journal, January 2019

  • Schlachter, Adrien; Bonnot, Antoine; Fortin, Daniel
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 30
  • DOI: 10.1039/c9cp02891a

Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays
journal, March 2019

  • Liu, Jianxi; Wang, Weijia; Wang, Danqing
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 13
  • DOI: 10.1073/pnas.1818902116