Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission
Molecules that exhibit emission in the solid state, especially those known as aggregation-induced emission (AIE) chromophores, have found applications in areas as varied as light-emitting diodes and biological sensors. Despite numerous studies, the mechanism of fluorescence quenching in AIE chromoph...
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American Chemical Society (ACS)
2013
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Online Access: | http://hdl.handle.net/1721.1/82041 https://orcid.org/0000-0003-1589-832X https://orcid.org/0000-0002-1262-1264 https://orcid.org/0000-0002-1100-0829 https://orcid.org/0000-0002-6708-7660 |
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author | Ong, Ta-Chung Michaelis, Vladimir K. Shustova, Natalia Cozzolino, Anthony Frank Griffin, Robert Guy Dinca, Mircea |
author2 | Massachusetts Institute of Technology. Department of Chemistry |
author_facet | Massachusetts Institute of Technology. Department of Chemistry Ong, Ta-Chung Michaelis, Vladimir K. Shustova, Natalia Cozzolino, Anthony Frank Griffin, Robert Guy Dinca, Mircea |
author_sort | Ong, Ta-Chung |
collection | MIT |
description | Molecules that exhibit emission in the solid state, especially those known as aggregation-induced emission (AIE) chromophores, have found applications in areas as varied as light-emitting diodes and biological sensors. Despite numerous studies, the mechanism of fluorescence quenching in AIE chromophores is still not completely understood. To this end, much interest has focused on understanding the low-frequency vibrational dynamics of prototypical systems, such as tetraphenylethylene (TPE), in the hope that such studies would provide more general principles toward the design of new sensors and electronic materials. We hereby show that a perdeuterated TPE-based metal–organic framework (MOF) serves as an excellent platform for studying the low-energy vibrational modes of AIE-type chromophores. In particular, we use solid-state [superscript 2]H and [superscript 13]C NMR experiments to investigate the phenyl ring dynamics of TPE cores that are coordinatively trapped inside a MOF and find a phenyl ring flipping energy barrier of 43(6) kJ/mol. DFT calculations are then used to deconvolute the electronic and steric contributions to this flipping barrier. Finally, we couple the NMR and DFT studies with variable-temperature X-ray diffraction experiments to propose that both the ethylenic C═C bond twist and the torsion of the phenyl rings are important for quenching emission in TPE, but that the former may gate the latter. To conclude, we use these findings to propose a set of design criteria for the development of tunable turn-on porous sensors constructed from AIE-type molecules, particularly as applied to the design of new multifunctional MOFs. |
first_indexed | 2024-09-23T13:04:28Z |
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institution | Massachusetts Institute of Technology |
language | en_US |
last_indexed | 2024-09-23T13:04:28Z |
publishDate | 2013 |
publisher | American Chemical Society (ACS) |
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spelling | mit-1721.1/820412022-10-01T12:53:36Z Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission Ong, Ta-Chung Michaelis, Vladimir K. Shustova, Natalia Cozzolino, Anthony Frank Griffin, Robert Guy Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology) Shustova, Natalia Ong, Ta-Chung Cozzolino, Anthony Frank Michaelis, Vladimir K. Griffin, Robert Guy Dinca, Mircea Molecules that exhibit emission in the solid state, especially those known as aggregation-induced emission (AIE) chromophores, have found applications in areas as varied as light-emitting diodes and biological sensors. Despite numerous studies, the mechanism of fluorescence quenching in AIE chromophores is still not completely understood. To this end, much interest has focused on understanding the low-frequency vibrational dynamics of prototypical systems, such as tetraphenylethylene (TPE), in the hope that such studies would provide more general principles toward the design of new sensors and electronic materials. We hereby show that a perdeuterated TPE-based metal–organic framework (MOF) serves as an excellent platform for studying the low-energy vibrational modes of AIE-type chromophores. In particular, we use solid-state [superscript 2]H and [superscript 13]C NMR experiments to investigate the phenyl ring dynamics of TPE cores that are coordinatively trapped inside a MOF and find a phenyl ring flipping energy barrier of 43(6) kJ/mol. DFT calculations are then used to deconvolute the electronic and steric contributions to this flipping barrier. Finally, we couple the NMR and DFT studies with variable-temperature X-ray diffraction experiments to propose that both the ethylenic C═C bond twist and the torsion of the phenyl rings are important for quenching emission in TPE, but that the former may gate the latter. To conclude, we use these findings to propose a set of design criteria for the development of tunable turn-on porous sensors constructed from AIE-type molecules, particularly as applied to the design of new multifunctional MOFs. United States. Dept. of Energy. Office of Basic Energy Sciences (Grant DE-SC0001088) United States. Dept. of Energy. Office of Basic Energy Sciences (Contract DE-AC02-06CH11357) National Science Foundation (U.S.) (Grant CHE-9808061) National Science Foundation (U.S.) (Grant DBI-9729592) National Science Foundation (U.S.) (Grant CHE-0946721) National Institutes of Health (U.S.) (Grant EB001960) National Institutes of Health (U.S.) (Grant EB002026) 2013-11-08T14:15:00Z 2013-11-08T14:15:00Z 2012-08 2012-06 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/82041 Shustova, Natalia B., Ta-Chung Ong, Anthony F. Cozzolino, Vladimir K. Michaelis, Robert G. Griffin, and Mircea Dincă. “Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission.” Journal of the American Chemical Society 134, no. 36 (September 12, 2012): 15061-15070. https://orcid.org/0000-0003-1589-832X https://orcid.org/0000-0002-1262-1264 https://orcid.org/0000-0002-1100-0829 https://orcid.org/0000-0002-6708-7660 en_US http://dx.doi.org/10.1021/ja306042w Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
spellingShingle | Ong, Ta-Chung Michaelis, Vladimir K. Shustova, Natalia Cozzolino, Anthony Frank Griffin, Robert Guy Dinca, Mircea Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission |
title | Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission |
title_full | Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission |
title_fullStr | Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission |
title_full_unstemmed | Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission |
title_short | Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal–Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission |
title_sort | phenyl ring dynamics in a tetraphenylethylene bridged metal organic framework implications for the mechanism of aggregation induced emission |
url | http://hdl.handle.net/1721.1/82041 https://orcid.org/0000-0003-1589-832X https://orcid.org/0000-0002-1262-1264 https://orcid.org/0000-0002-1100-0829 https://orcid.org/0000-0002-6708-7660 |
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