Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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]
+ Show Author Affiliations
  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 Laboratory (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.
Copy to clipboard
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. https://doi.org/10.1021/jacs.6b01345
Copy to clipboard
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. https://doi.org/10.1021/jacs.6b01345.
Copy to clipboard
@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 = {Mon Jan 11 00:00:00 EST 2016},
month = {Mon Jan 11 00:00:00 EST 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.6b01345
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 109 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

CHLOROPHYLLS IN POLYMERS. I. STATE OF CHLOROPHYLL a IN UNSTRETCHED POLYMER SYSTEMS
journal, August 1995

Excited State Interactions in Electropolymerized Thin Films of Ru II , Os II , and Zn II Polypyridyl Complexes
journal, June 1997

  • Devenney, Martin; Worl, Laura A.; Gould, Sharon
  • The Journal of Physical Chemistry A, Vol. 101, Issue 25
  • DOI: 10.1021/jp971076t

Light-Harvesting Metal–Organic Frameworks (MOFs) Efficient Strut-to-Strut Energy Transfer in Bodipy and Porphyrin-Based MOFs
journal, October 2011

  • Lee, Chang Yeon; Farha, Omar K.; Hong, Bong Jin
  • Journal of the American Chemical Society, Vol. 133, Issue 40, p. 15858-15861
  • DOI: 10.1021/ja206029a

Nanoscale Light-Harvesting Metal-Organic Frameworks
journal, May 2011

  • Zhang, Xuanjun; Ballem, Mohamed Ali; Hu, Zhang-Jun
  • Angewandte Chemie International Edition, Vol. 50, Issue 25
  • DOI: 10.1002/anie.201007277

Structure-Property relationships for exciton transfer in conjugated polymers
journal, February 2011

  • Andrew, Trisha L.; Swager, Timothy M.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 7
  • DOI: 10.1002/polb.22207

Confinement of pyridinium hemicyanine dye within an anionic metal-organic framework for two-photon-pumped lasing
journal, October 2013

  • Yu, Jiancan; Cui, Yuanjing; Xu, Hui
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3719

A Luminescent Dye@MOF Platform: Emission Fingerprint Relationships of Volatile Organic Molecules
journal, January 2014

  • Dong, Ming-Jie; Zhao, Min; Ou, Sha
  • Angewandte Chemie International Edition, Vol. 53, Issue 6
  • DOI: 10.1002/anie.201307331

Triplet Excitation Energy Dynamics in Metal–Organic Frameworks
journal, June 2013

  • Lin, Jiaxing; Hu, Xiangqian; Zhang, Peng
  • The Journal of Physical Chemistry C, Vol. 117, Issue 43
  • DOI: 10.1021/jp401515r

Photoelectric Covalent Organic Frameworks: Converting Open Lattices into Ordered Donor–Acceptor Heterojunctions
journal, July 2014

  • Chen, Long; Furukawa, Ko; Gao, Jia
  • Journal of the American Chemical Society, Vol. 136, Issue 28
  • DOI: 10.1021/ja502692w

Luminescent Functional Metal–Organic Frameworks
journal, June 2011

  • Cui, Yuanjing; Yue, Yanfeng; Qian, Guodong
  • Chemical Reviews, Vol. 112, Issue 2
  • DOI: 10.1021/cr200101d

Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex
journal, June 2015

  • Maza, William A.; Padilla, Roberto; Morris, Amanda J.
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b03071

Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels
journal, May 2013

Rapid energy transfer in non-porous metal–organic frameworks with caged Ru(bpy)32+ chromophores: oxygen trapping and luminescence quenching
journal, January 2013

  • Kent, Caleb A.; Liu, Demin; Ito, Akitaka
  • Journal of Materials Chemistry A, Vol. 1, Issue 47
  • DOI: 10.1039/c3ta14009a

Light Harvesting and Energy Transfer in Novel Convergently Constructed Dendrimers
journal, May 1999

Layer-by-Layer Fabrication of Oriented Porous Thin Films Based on Porphyrin-Containing Metal–Organic Frameworks
journal, October 2013

  • So, Monica C.; Jin, Shengye; Son, Ho-Jin
  • Journal of the American Chemical Society, Vol. 135, Issue 42
  • DOI: 10.1021/ja4078705

Novel metal–organic framework linkers for light harvesting applications
journal, January 2014

  • Foster, Michael E.; Azoulay, Jason D.; Wong, Bryan M.
  • Chem. Sci., Vol. 5, Issue 5
  • DOI: 10.1039/c4sc00333k

Light Harvesting in Microscale Metal–Organic Frameworks by Energy Migration and Interfacial Electron Transfer Quenching
journal, August 2011

  • Kent, Caleb A.; Liu, Demin; Ma, Liqing
  • Journal of the American Chemical Society, Vol. 133, Issue 33
  • DOI: 10.1021/ja204214t

The 17-Propionate Function of (Bacterio)chlorophylls: Biological Implication of Their Long Esterifying Chains in Photosynthetic Systems
journal, January 2006

Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems
journal, December 2009

  • Wasielewski, Michael R.
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar9001735

Energy Transfer on Demand: Photoswitch-Directed Behavior of Metal–Porphyrin Frameworks
journal, August 2014

  • Williams, Derek E.; Rietman, Joseph A.; Maier, Josef M.
  • Journal of the American Chemical Society, Vol. 136, Issue 34
  • DOI: 10.1021/ja505589d

Crystal structure of spinach major light-harvesting complex at 2.72 Å resolution
journal, March 2004

  • Liu, Zhenfeng; Yan, Hanchi; Wang, Kebin
  • Nature, Vol. 428, Issue 6980
  • DOI: 10.1038/nature02373

Intermolecular Energy Transfer across Nanocrystalline Semiconductor Surfaces
journal, February 2006

  • Higgins, Gerard T.; Bergeron, Bryan V.; Hasselmann, Georg M.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 6
  • DOI: 10.1021/jp0543680

Discrete Cyclic Porphyrin Arrays as Artificial Light-Harvesting Antenna
journal, December 2009

  • Aratani, Naoki; Kim, Dongho; Osuka, Atsuhiro
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar9001697

Amplified Luminescence Quenching of Phosphorescent Metal–Organic Frameworks
journal, February 2012

  • Kent, Caleb A.; Liu, Demin; Meyer, Thomas J.
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja211271m

Metal–organic framework materials for light-harvesting and energy transfer
journal, January 2015

  • So, Monica C.; Wiederrecht, Gary P.; Mondloch, Joseph E.
  • Chemical Communications, Vol. 51, Issue 17
  • DOI: 10.1039/C4CC09596K

Luminescent metal–organic frameworks for chemical sensing and explosive detection
journal, January 2014

  • Hu, Zhichao; Deibert, Benjamin J.; Li, Jing
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00010B

Dual-Emitting MOF⊃Dye Composite for Ratiometric Temperature Sensing
journal, January 2015

Light Harvesting in Photosystem I: Modeling Based on the 2.5-Å Structure of Photosystem I from Synechococcus elongatus
journal, July 2002

Design and engineering of photosynthetic light-harvesting and electron transfer using length, time, and energy scales
journal, February 2006

  • Noy, Dror; Moser, Christopher C.; Dutton, P. Leslie
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1757, Issue 2
  • DOI: 10.1016/j.bbabio.2005.11.010

Zinc-Adeninate Metal−Organic Framework for Aqueous Encapsulation and Sensitization of Near-infrared and Visible Emitting Lanthanide Cations
journal, February 2011

  • An, Jihyun; Shade, Chad M.; Chengelis-Czegan, Demetra A.
  • Journal of the American Chemical Society, Vol. 133, Issue 5
  • DOI: 10.1021/ja109103t

Triarylborane-terminalized branched π-conjugative dyes: Synthesis, structure and optoelectronic properties
journal, August 2014

Turn-On Fluorescence in Tetraphenylethylene-Based Metal–Organic Frameworks: An Alternative to Aggregation-Induced Emission
journal, December 2011

  • Shustova, Natalia B.; McCarthy, Brian D.; Dincă, Mircea
  • Journal of the American Chemical Society, Vol. 133, Issue 50
  • DOI: 10.1021/ja209327q

Frameworks for Extended Solids: Geometrical Design Principles
journal, June 2000

  • O'Keeffe, M.; Eddaoudi, M.; Li, Hailian
  • Journal of Solid State Chemistry, Vol. 152, Issue 1, p. 3-20
  • DOI: 10.1006/jssc.2000.8723

Dual-Emission from a Single-Phase Eu–Ag Metal–Organic Framework: An Alternative Way to Get White-Light Phosphor
journal, May 2012

  • Liu, Yu; Pan, Mei; Yang, Qing-Yuan
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm3008254

Crystallized Frameworks with Giant Pores:  Are There Limits to the Possible?
journal, April 2005

  • Férey, Gérard; Mellot-Draznieks, Caroline; Serre, Christian
  • Accounts of Chemical Research, Vol. 38, Issue 4
  • DOI: 10.1021/ar040163i

Exciton diffusion in organic photovoltaic cells
journal, January 2014

  • Menke, S. Matthew; Holmes, Russell J.
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE42444H

Photoinduced Energy Transfer between Ruthenium and Osmium tris-Bipyridine Complexes Covalently Pillared into γ-ZrP
journal, January 2003

  • Odobel, Fabrice; Massiot, Dominique; Harrison, Benjamin S.
  • Langmuir, Vol. 19, Issue 1
  • DOI: 10.1021/la026029t

Exciton Migration in Molecular Crystals
journal, June 1971

  • Grover, M.; Silbey, R.
  • The Journal of Chemical Physics, Vol. 54, Issue 11
  • DOI: 10.1063/1.1674761

Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal–Organic Frameworks
journal, December 2012

  • Son, Ho-Jin; Jin, Shengye; Patwardhan, Sameer
  • Journal of the American Chemical Society, Vol. 135, Issue 2
  • DOI: 10.1021/ja310596a

Approaches to Calculation of Exciton Interaction Energies for a Molecular Dimer
journal, December 2004

  • Howard, I. A.; Zutterman, F.; Deroover, G.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 50
  • DOI: 10.1021/jp040417h

Coordination polymers for energy transfer: Preparations, properties, sensing applications, and perspectives
journal, February 2015

Chemical Sensors Based on Amplifying Fluorescent Conjugated Polymers
journal, April 2007

  • Thomas, Samuel W.; Joly, Guy D.; Swager, Timothy M.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr0501339

Stoichiometric determination of pheophytin in photosystem II of oxygenic photosynthesis
journal, January 1986

  • Murata, N.; Araki, S.; Fujita, Y.
  • Photosynthesis Research, Vol. 9, Issue 1-2
  • DOI: 10.1007/BF00029732

A Luminescent Microporous Metal-Organic Framework for the Fast and Reversible Detection of High Explosives
journal, January 2009

  • Lan, Anjian; Li, Kunhao; Wu, Haohan
  • Angewandte Chemie International Edition, Vol. 48, Issue 13, p. 2334-2338
  • DOI: 10.1002/anie.200804853

Gas detection by structural variations of fluorescent guest molecules in a flexible porous coordination polymer
journal, September 2011

  • Yanai, Nobuhiro; Kitayama, Koji; Hijikata, Yuh
  • Nature Materials, Vol. 10, Issue 10, p. 787-793
  • DOI: 10.1038/nmat3104

Dynamics of Light Harvesting in Photosynthesis
journal, May 2009

Solvothermal Growth and Photophysical Characterization of a Ruthenium(II) Tris(2,2′-Bipyridine)-Doped Zirconium UiO-67 Metal Organic Framework Thin Film
journal, June 2014

  • Maza, William A.; Ahrenholtz, Spencer R.; Epley, Charity C.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 26
  • DOI: 10.1021/jp5034195

Crystalline molecular flasks
journal, April 2011

  • Inokuma, Yasuhide; Kawano, Masaki; Fujita, Makoto
  • Nature Chemistry, Vol. 3, Issue 5
  • DOI: 10.1038/nchem.1031

Photochromic Metal-Organic Frameworks: Reversible Control of Singlet Oxygen Generation
journal, December 2014

  • Park, Jihye; Feng, Dawei; Yuan, Shuai
  • Angewandte Chemie International Edition, Vol. 54, Issue 2
  • DOI: 10.1002/anie.201408862

Excitation energy transfer, trapping and annihilation in photosynthetic systems
journal, June 1985

Förster Energy Transfer Theory as Reflected in the Structures of Photosynthetic Light‐Harvesting Systems
journal, February 2011

Ultrafast excitation energy transfer dynamics in photosynthetic pigment–protein complexes
journal, March 2001

Distance and Orientation Dependence of Excitation Transfer Rates in Conjugated Systems:  Beyond the Förster Theory
journal, July 2004

  • Wong, Kim F.; Bagchi, Biman; Rossky, Peter J.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 27
  • DOI: 10.1021/jp037724s

Energy Transfer Dynamics in Metal−Organic Frameworks
journal, September 2010

  • Kent, Caleb A.; Mehl, Brian P.; Ma, Liqing
  • Journal of the American Chemical Society, Vol. 132, Issue 37
  • DOI: 10.1021/ja102804s

Theoretical Study of the Optical Properties of Artificial Self-Assembled Zinc Chlorins
journal, October 2010

  • Patwardhan, Sameer; Sengupta, Sanchita; Würthner, Frank
  • The Journal of Physical Chemistry C, Vol. 114, Issue 48
  • DOI: 10.1021/jp107184y

Energy Transfer from Quantum Dots to Metal–Organic Frameworks for Enhanced Light Harvesting
journal, January 2013

  • Jin, Shengye; Son, Ho-Jin; Farha, Omar K.
  • Journal of the American Chemical Society, Vol. 135, Issue 3
  • DOI: 10.1021/ja3097114
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: