Expansion of Photostable Luminescent Radicals by Meta‐Substitution

Polychlorinated pyridyldiphenylmethyl radicals having substituents meta to the position bearing the carbon‐centered radical (α‐carbon) are synthesized. All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4‐chl...

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Veröffentlicht in:Chemistry, an Asian journal an Asian journal, 2021-09, Vol.16 (17), p.2538-2544
Hauptverfasser: Hattori, Yohei, Tsubaki, Shunsuke, Matsuoka, Ryota, Kusamoto, Tetsuro, Nishihara, Hiroshi, Uchida, Kingo
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container_issue 17
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container_title Chemistry, an Asian journal
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Tsubaki, Shunsuke
Matsuoka, Ryota
Kusamoto, Tetsuro
Nishihara, Hiroshi
Uchida, Kingo
description Polychlorinated pyridyldiphenylmethyl radicals having substituents meta to the position bearing the carbon‐centered radical (α‐carbon) are synthesized. All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4‐chlorophenyl, or 2‐pyridyl substituents are enhanced in chloroform, while the emission of the radicals with 2‐thienyl or 2‐furyl substituents are quenched in chloroform. DFT and TD‐DFT calculations indicate that the first doublet excited states of the former are locally excited, while the first doublet excited states of the latter are charge transfer states from the π‐electron‐donating substituent to the accepting radical. The latter also show much higher photostability under 370‐nm light irradiation compared with the first reported photostable fluorescent radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), with pronounced bathochromic shifts of the fluorescence. To clarify the role of meta‐substituents on stable luminescent radicals, six novel stable radicals (mBr2−F2PyBTM, mPh2−F2PyBTM, mClPh2−F2PyBTM, mPy2−F2PyBTM, mTh2−F2PyBTM, mFu2−F2PyBTM) were synthesized. All of them are stable in solutions at room temperature and fluorescent in cyclohexane. When the meta‐substituent becomes highly electron‐rich, the fluorescence was red‐shifted, and quenching and photostability were enhanced.
doi_str_mv 10.1002/asia.202100612
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All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4‐chlorophenyl, or 2‐pyridyl substituents are enhanced in chloroform, while the emission of the radicals with 2‐thienyl or 2‐furyl substituents are quenched in chloroform. DFT and TD‐DFT calculations indicate that the first doublet excited states of the former are locally excited, while the first doublet excited states of the latter are charge transfer states from the π‐electron‐donating substituent to the accepting radical. The latter also show much higher photostability under 370‐nm light irradiation compared with the first reported photostable fluorescent radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), with pronounced bathochromic shifts of the fluorescence. To clarify the role of meta‐substituents on stable luminescent radicals, six novel stable radicals (mBr2−F2PyBTM, mPh2−F2PyBTM, mClPh2−F2PyBTM, mPy2−F2PyBTM, mTh2−F2PyBTM, mFu2−F2PyBTM) were synthesized. All of them are stable in solutions at room temperature and fluorescent in cyclohexane. 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All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4‐chlorophenyl, or 2‐pyridyl substituents are enhanced in chloroform, while the emission of the radicals with 2‐thienyl or 2‐furyl substituents are quenched in chloroform. DFT and TD‐DFT calculations indicate that the first doublet excited states of the former are locally excited, while the first doublet excited states of the latter are charge transfer states from the π‐electron‐donating substituent to the accepting radical. The latter also show much higher photostability under 370‐nm light irradiation compared with the first reported photostable fluorescent radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), with pronounced bathochromic shifts of the fluorescence. To clarify the role of meta‐substituents on stable luminescent radicals, six novel stable radicals (mBr2−F2PyBTM, mPh2−F2PyBTM, mClPh2−F2PyBTM, mPy2−F2PyBTM, mTh2−F2PyBTM, mFu2−F2PyBTM) were synthesized. All of them are stable in solutions at room temperature and fluorescent in cyclohexane. When the meta‐substituent becomes highly electron‐rich, the fluorescence was red‐shifted, and quenching and photostability were enhanced.</description><subject>Carbon</subject><subject>Charge transfer</subject><subject>Chemistry</subject><subject>Chloroform</subject><subject>Cyclohexane</subject><subject>density functional calculations</subject><subject>donor-acceptor systems</subject><subject>Excitation</subject><subject>Fluorescence</subject><subject>Light irradiation</subject><subject>Methyl radicals</subject><subject>photostability</subject><subject>radicals</subject><issn>1861-4728</issn><issn>1861-471X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqFkM9KAzEQhxdRsFavnhe8eGmdZPP3WGrVQkWxCt6W7G6CKdtN3WTR3nwEn9EnMaVSwYunmWG-bxh-SXKKYIgA8IXyVg0x4DgwhPeSHhIMDQhHz_u7HovD5Mj7BQDFIEUvuZy8r1TjrWtSZ9L7FxecD6qodTrrlrbRvtRNSB9UZUtV-7RYp7c6qK-Pz3lX-GBDF6J6nByYuNUnP7WfPF1NHsc3g9nd9XQ8mg1KghgeZIIKWXFhCgVEVUrKkosMBK04IZxrwQArkBSMIZUyuKJYGJNBqRUznKGsn5xv765a99ppH_KljQ_WtWq063yOKcWSCwokomd_0IXr2iZ-FynGJWEgIVLDLVW2zvtWm3zV2qVq1zmCfBNqvgk134UaBbkV3myt1__Q-Wg-Hf263-0Le2s</recordid><startdate>20210901</startdate><enddate>20210901</enddate><creator>Hattori, Yohei</creator><creator>Tsubaki, Shunsuke</creator><creator>Matsuoka, Ryota</creator><creator>Kusamoto, Tetsuro</creator><creator>Nishihara, Hiroshi</creator><creator>Uchida, Kingo</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9281-0403</orcidid></search><sort><creationdate>20210901</creationdate><title>Expansion of Photostable Luminescent Radicals by Meta‐Substitution</title><author>Hattori, Yohei ; Tsubaki, Shunsuke ; Matsuoka, Ryota ; Kusamoto, Tetsuro ; Nishihara, Hiroshi ; Uchida, Kingo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4162-38589d78fba04ada99c783085d74477e8602a0950ff4daf2d528ff30cea6f7613</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Carbon</topic><topic>Charge transfer</topic><topic>Chemistry</topic><topic>Chloroform</topic><topic>Cyclohexane</topic><topic>density functional calculations</topic><topic>donor-acceptor systems</topic><topic>Excitation</topic><topic>Fluorescence</topic><topic>Light irradiation</topic><topic>Methyl radicals</topic><topic>photostability</topic><topic>radicals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hattori, Yohei</creatorcontrib><creatorcontrib>Tsubaki, Shunsuke</creatorcontrib><creatorcontrib>Matsuoka, Ryota</creatorcontrib><creatorcontrib>Kusamoto, Tetsuro</creatorcontrib><creatorcontrib>Nishihara, Hiroshi</creatorcontrib><creatorcontrib>Uchida, Kingo</creatorcontrib><collection>CrossRef</collection><collection>ProQuest Health &amp; Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry, an Asian journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hattori, Yohei</au><au>Tsubaki, Shunsuke</au><au>Matsuoka, Ryota</au><au>Kusamoto, Tetsuro</au><au>Nishihara, Hiroshi</au><au>Uchida, Kingo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Expansion of Photostable Luminescent Radicals by Meta‐Substitution</atitle><jtitle>Chemistry, an Asian journal</jtitle><date>2021-09-01</date><risdate>2021</risdate><volume>16</volume><issue>17</issue><spage>2538</spage><epage>2544</epage><pages>2538-2544</pages><issn>1861-4728</issn><eissn>1861-471X</eissn><abstract>Polychlorinated pyridyldiphenylmethyl radicals having substituents meta to the position bearing the carbon‐centered radical (α‐carbon) are synthesized. All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4‐chlorophenyl, or 2‐pyridyl substituents are enhanced in chloroform, while the emission of the radicals with 2‐thienyl or 2‐furyl substituents are quenched in chloroform. DFT and TD‐DFT calculations indicate that the first doublet excited states of the former are locally excited, while the first doublet excited states of the latter are charge transfer states from the π‐electron‐donating substituent to the accepting radical. The latter also show much higher photostability under 370‐nm light irradiation compared with the first reported photostable fluorescent radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), with pronounced bathochromic shifts of the fluorescence. 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source Wiley Online Library Journals Frontfile Complete
subjects Carbon
Charge transfer
Chemistry
Chloroform
Cyclohexane
density functional calculations
donor-acceptor systems
Excitation
Fluorescence
Light irradiation
Methyl radicals
photostability
radicals
title Expansion of Photostable Luminescent Radicals by Meta‐Substitution
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