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

Zhang, Qiongqiong; Zhang, Cankun; Cao, Lingyun; Wang, Zi; An, Bing; Lin, Zekai; Huang, Ruiyun; Zhang, Zhiming; Wang, Cheng; Lin, Wenbin

doi:10.1021/jacs.6b01345

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

Journal Article · Mon Jan 11 00:00:00 EST 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b01345· OSTI ID:1247615

Zhang, Qiongqiong ^[1]; Zhang, Cankun ^[1]; Cao, Lingyun ^[1]; Wang, Zi ^[1]; An, Bing ^[1]; Lin, Zekai ^[2]; Huang, Ruiyun ^[1]; Zhang, Zhiming ^[1]; Wang, Cheng ^[1]; Lin, Wenbin ^[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
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

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: 21471126; NSF/CHE-1346572; AC02-06CH11357

OSTI ID:: 1247615

Alternate ID(s):: OSTI ID: 1337702

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 138 Journal Issue: 16; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 109 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dyes and pigments
Excitons
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Title: Förster Energy Transport in Metal–Organic Frameworks Is Beyond Step-by-Step Hopping

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