Loading…
Role of the Perfluoro Effect in the Selective Photochemical Isomerization of Hexafluorobenzene
Hexafluorobenzene and many of its derivatives exhibit a chemoselective photochemical isomerization, resulting in highly strained, Dewar-type bicyclohexenes. While the changes in absorption and emission associated with benzene hexafluorination have been attributed to the so-called “perfluoro effect”,...
Saved in:
Published in: | Journal of the American Chemical Society 2021-05, Vol.143 (18), p.7002-7012 |
---|---|
Main Authors: | , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
cited_by | cdi_FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153 |
---|---|
cites | cdi_FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153 |
container_end_page | 7012 |
container_issue | 18 |
container_start_page | 7002 |
container_title | Journal of the American Chemical Society |
container_volume | 143 |
creator | Cox, Jordan M Bain, Matthew Kellogg, Michael Bradforth, Stephen E Lopez, Steven A |
description | Hexafluorobenzene and many of its derivatives exhibit a chemoselective photochemical isomerization, resulting in highly strained, Dewar-type bicyclohexenes. While the changes in absorption and emission associated with benzene hexafluorination have been attributed to the so-called “perfluoro effect”, the resulting electronic structure and photochemical reactivity of hexafluorobenzene is still unclear. We now use a combination of ultrafast time-resolved spectroscopy, multiconfigurational computations, and non-adiabatic dynamics simulations to develop a holistic description of the absorption, emission, and photochemical dynamics of the 4π-electrocyclic ring-closing of hexafluorobenzene and the fluorination effect along the reaction coordinate. Our calculations suggest that the electron-withdrawing fluorine substituents induce a vibronic coupling between the lowest-energy 1B2u (ππ*) and 1E1g (πσ*) excited states by selectively stabilizing the σ-type states. The vibronic coupling occurs along vibrational modes of e2u symmetry which distorts the excited-state minimum geometry resulting in the experimentally broad, featureless absorption bands, and a ∼100 nm Stokes shift in fluorescencein stark contrast to benzene. Finally, the vibronic coupling is shown to simultaneously destabilize the reaction pathway toward hexafluoro-benzvalene and promote molecular vibrations along the 4π ring-closing pathway, resulting in the chemoselectivity for hexafluoro-Dewar-benzene. |
doi_str_mv | 10.1021/jacs.1c01506 |
format | article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_2521493444</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2521493444</sourcerecordid><originalsourceid>FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153</originalsourceid><addsrcrecordid>eNptkDtPwzAURi0EoqWwMaOMDKT4mdojqgqtVAnEYyVynGs1VRIXO0HQX09CCyxM1mede67uh9A5wWOCKbleaxPGxGAicHKAhkRQHAtCk0M0xBjTeCITNkAnIay7yKkkx2jAmGJywtUQvT66EiJno2YF0QN4W7bOu2hmLZgmKurv_ycou1S8d8TKNc6soCqMLqNFcBX4YqubwtW9ZA4femfIoN5CDafoyOoywNn-HaGX29nzdB4v7-8W05tlrBnlTUxzrnLDLEmM4pnSOeFaZjTH1NguWUE4YJpLI8WEG2FVYkGJROaZlFITwUbocufdePfWQmjSqggGylLX4NqQUkEJV4xz3qFXO9R4F4IHm258UWn_mRKc9o2mfaPpvtEOv9ib26yC_Bf-qfBvdT-1dq2vu0P_d30BroSAAA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2521493444</pqid></control><display><type>article</type><title>Role of the Perfluoro Effect in the Selective Photochemical Isomerization of Hexafluorobenzene</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)</source><creator>Cox, Jordan M ; Bain, Matthew ; Kellogg, Michael ; Bradforth, Stephen E ; Lopez, Steven A</creator><creatorcontrib>Cox, Jordan M ; Bain, Matthew ; Kellogg, Michael ; Bradforth, Stephen E ; Lopez, Steven A</creatorcontrib><description>Hexafluorobenzene and many of its derivatives exhibit a chemoselective photochemical isomerization, resulting in highly strained, Dewar-type bicyclohexenes. While the changes in absorption and emission associated with benzene hexafluorination have been attributed to the so-called “perfluoro effect”, the resulting electronic structure and photochemical reactivity of hexafluorobenzene is still unclear. We now use a combination of ultrafast time-resolved spectroscopy, multiconfigurational computations, and non-adiabatic dynamics simulations to develop a holistic description of the absorption, emission, and photochemical dynamics of the 4π-electrocyclic ring-closing of hexafluorobenzene and the fluorination effect along the reaction coordinate. Our calculations suggest that the electron-withdrawing fluorine substituents induce a vibronic coupling between the lowest-energy 1B2u (ππ*) and 1E1g (πσ*) excited states by selectively stabilizing the σ-type states. The vibronic coupling occurs along vibrational modes of e2u symmetry which distorts the excited-state minimum geometry resulting in the experimentally broad, featureless absorption bands, and a ∼100 nm Stokes shift in fluorescencein stark contrast to benzene. Finally, the vibronic coupling is shown to simultaneously destabilize the reaction pathway toward hexafluoro-benzvalene and promote molecular vibrations along the 4π ring-closing pathway, resulting in the chemoselectivity for hexafluoro-Dewar-benzene.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.1c01506</identifier><identifier>PMID: 33938749</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2021-05, Vol.143 (18), p.7002-7012</ispartof><rights>2021 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153</citedby><cites>FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153</cites><orcidid>0000-0002-3476-2455 ; 0000-0002-8418-3638 ; 0000-0002-6164-3347</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33938749$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Cox, Jordan M</creatorcontrib><creatorcontrib>Bain, Matthew</creatorcontrib><creatorcontrib>Kellogg, Michael</creatorcontrib><creatorcontrib>Bradforth, Stephen E</creatorcontrib><creatorcontrib>Lopez, Steven A</creatorcontrib><title>Role of the Perfluoro Effect in the Selective Photochemical Isomerization of Hexafluorobenzene</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Hexafluorobenzene and many of its derivatives exhibit a chemoselective photochemical isomerization, resulting in highly strained, Dewar-type bicyclohexenes. While the changes in absorption and emission associated with benzene hexafluorination have been attributed to the so-called “perfluoro effect”, the resulting electronic structure and photochemical reactivity of hexafluorobenzene is still unclear. We now use a combination of ultrafast time-resolved spectroscopy, multiconfigurational computations, and non-adiabatic dynamics simulations to develop a holistic description of the absorption, emission, and photochemical dynamics of the 4π-electrocyclic ring-closing of hexafluorobenzene and the fluorination effect along the reaction coordinate. Our calculations suggest that the electron-withdrawing fluorine substituents induce a vibronic coupling between the lowest-energy 1B2u (ππ*) and 1E1g (πσ*) excited states by selectively stabilizing the σ-type states. The vibronic coupling occurs along vibrational modes of e2u symmetry which distorts the excited-state minimum geometry resulting in the experimentally broad, featureless absorption bands, and a ∼100 nm Stokes shift in fluorescencein stark contrast to benzene. Finally, the vibronic coupling is shown to simultaneously destabilize the reaction pathway toward hexafluoro-benzvalene and promote molecular vibrations along the 4π ring-closing pathway, resulting in the chemoselectivity for hexafluoro-Dewar-benzene.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNptkDtPwzAURi0EoqWwMaOMDKT4mdojqgqtVAnEYyVynGs1VRIXO0HQX09CCyxM1mede67uh9A5wWOCKbleaxPGxGAicHKAhkRQHAtCk0M0xBjTeCITNkAnIay7yKkkx2jAmGJywtUQvT66EiJno2YF0QN4W7bOu2hmLZgmKurv_ycou1S8d8TKNc6soCqMLqNFcBX4YqubwtW9ZA4femfIoN5CDafoyOoywNn-HaGX29nzdB4v7-8W05tlrBnlTUxzrnLDLEmM4pnSOeFaZjTH1NguWUE4YJpLI8WEG2FVYkGJROaZlFITwUbocufdePfWQmjSqggGylLX4NqQUkEJV4xz3qFXO9R4F4IHm258UWn_mRKc9o2mfaPpvtEOv9ib26yC_Bf-qfBvdT-1dq2vu0P_d30BroSAAA</recordid><startdate>20210512</startdate><enddate>20210512</enddate><creator>Cox, Jordan M</creator><creator>Bain, Matthew</creator><creator>Kellogg, Michael</creator><creator>Bradforth, Stephen E</creator><creator>Lopez, Steven A</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-3476-2455</orcidid><orcidid>https://orcid.org/0000-0002-8418-3638</orcidid><orcidid>https://orcid.org/0000-0002-6164-3347</orcidid></search><sort><creationdate>20210512</creationdate><title>Role of the Perfluoro Effect in the Selective Photochemical Isomerization of Hexafluorobenzene</title><author>Cox, Jordan M ; Bain, Matthew ; Kellogg, Michael ; Bradforth, Stephen E ; Lopez, Steven A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cox, Jordan M</creatorcontrib><creatorcontrib>Bain, Matthew</creatorcontrib><creatorcontrib>Kellogg, Michael</creatorcontrib><creatorcontrib>Bradforth, Stephen E</creatorcontrib><creatorcontrib>Lopez, Steven A</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cox, Jordan M</au><au>Bain, Matthew</au><au>Kellogg, Michael</au><au>Bradforth, Stephen E</au><au>Lopez, Steven A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Role of the Perfluoro Effect in the Selective Photochemical Isomerization of Hexafluorobenzene</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2021-05-12</date><risdate>2021</risdate><volume>143</volume><issue>18</issue><spage>7002</spage><epage>7012</epage><pages>7002-7012</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Hexafluorobenzene and many of its derivatives exhibit a chemoselective photochemical isomerization, resulting in highly strained, Dewar-type bicyclohexenes. While the changes in absorption and emission associated with benzene hexafluorination have been attributed to the so-called “perfluoro effect”, the resulting electronic structure and photochemical reactivity of hexafluorobenzene is still unclear. We now use a combination of ultrafast time-resolved spectroscopy, multiconfigurational computations, and non-adiabatic dynamics simulations to develop a holistic description of the absorption, emission, and photochemical dynamics of the 4π-electrocyclic ring-closing of hexafluorobenzene and the fluorination effect along the reaction coordinate. Our calculations suggest that the electron-withdrawing fluorine substituents induce a vibronic coupling between the lowest-energy 1B2u (ππ*) and 1E1g (πσ*) excited states by selectively stabilizing the σ-type states. The vibronic coupling occurs along vibrational modes of e2u symmetry which distorts the excited-state minimum geometry resulting in the experimentally broad, featureless absorption bands, and a ∼100 nm Stokes shift in fluorescencein stark contrast to benzene. Finally, the vibronic coupling is shown to simultaneously destabilize the reaction pathway toward hexafluoro-benzvalene and promote molecular vibrations along the 4π ring-closing pathway, resulting in the chemoselectivity for hexafluoro-Dewar-benzene.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>33938749</pmid><doi>10.1021/jacs.1c01506</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-3476-2455</orcidid><orcidid>https://orcid.org/0000-0002-8418-3638</orcidid><orcidid>https://orcid.org/0000-0002-6164-3347</orcidid></addata></record> |
fulltext | fulltext |
identifier | ISSN: 0002-7863 |
ispartof | Journal of the American Chemical Society, 2021-05, Vol.143 (18), p.7002-7012 |
issn | 0002-7863 1520-5126 |
language | eng |
recordid | cdi_proquest_miscellaneous_2521493444 |
source | American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list) |
title | Role of the Perfluoro Effect in the Selective Photochemical Isomerization of Hexafluorobenzene |
url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-23T12%3A07%3A32IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Role%20of%20the%20Perfluoro%20Effect%20in%20the%20Selective%20Photochemical%20Isomerization%20of%20Hexafluorobenzene&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Cox,%20Jordan%20M&rft.date=2021-05-12&rft.volume=143&rft.issue=18&rft.spage=7002&rft.epage=7012&rft.pages=7002-7012&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/jacs.1c01506&rft_dat=%3Cproquest_cross%3E2521493444%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a324t-2d49dc3f16c94b9ad14a8b2d02cf9adf514e02d8c8574c5f96fe9568db888a153%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=2521493444&rft_id=info:pmid/33938749&rfr_iscdi=true |