Controlling excited-state dynamics protonation of naphthalene-based azo dyes
Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions. This work explores the impact of protonation on the photophysics of four naphthalene-based azo dyes. The p K a value of the dyes increases proportio...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2024-04, Vol.26 (14), p.184-1813 |
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| creator | Martin, Shea M Hamburger, Robert C Huang, Tao Fredin, Lisa A Young, Elizabeth R |
| description | Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions. This work explores the impact of protonation on the photophysics of four naphthalene-based azo dyes. The p
K
a
value of the dyes increases proportionally with decreasing Hammett parameter of
p
-phenyl substituents from 8.1 (R = -H,
σ
= 0) to 10.6 (R = -NMe2,
σ
= -0.83) in acetonitrile. Protonation of the dyes shuts down the steady-state photoisomerization observed in the unprotonated moieties. Fluorescence measurements reveal a lower quantum yield with more electron-donating
p
-phenyl substituents, with overall lower fluorescence quantum yields than the unprotonated dyes. Transient absorption spectroscopy reveals four excited-state lifetimes ( |
| doi_str_mv | 10.1039/d4cp00242c |
| format | Article |
| fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_d4cp00242c</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>d4cp00242c</sourcerecordid><originalsourceid>FETCH-rsc_primary_d4cp00242c3</originalsourceid><addsrcrecordid>eNqFjr0OwiAYRYnRxN_F3YQXqELBaudG4-Do3nwCtRgKBBisT6-D0dHpnuSc4SK0pGRNCSs3kgtPSM5zMUATyguWlWTPh1_eFWM0jfFOCKFbyiboXDmbgjNG2xtWD6GTkllMkBSWvYVOi4h9cMlZSNpZ7BpswbepBaOsyq4QlcTwdO9axTkaNWCiWnx2hlbHw6U6ZSGK2gfdQejr30X2z78AVnJAJw</addsrcrecordid><sourcetype>Publisher</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Controlling excited-state dynamics protonation of naphthalene-based azo dyes</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Martin, Shea M ; Hamburger, Robert C ; Huang, Tao ; Fredin, Lisa A ; Young, Elizabeth R</creator><creatorcontrib>Martin, Shea M ; Hamburger, Robert C ; Huang, Tao ; Fredin, Lisa A ; Young, Elizabeth R</creatorcontrib><description>Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions. This work explores the impact of protonation on the photophysics of four naphthalene-based azo dyes. The p
K
a
value of the dyes increases proportionally with decreasing Hammett parameter of
p
-phenyl substituents from 8.1 (R = -H,
σ
= 0) to 10.6 (R = -NMe2,
σ
= -0.83) in acetonitrile. Protonation of the dyes shuts down the steady-state photoisomerization observed in the unprotonated moieties. Fluorescence measurements reveal a lower quantum yield with more electron-donating
p
-phenyl substituents, with overall lower fluorescence quantum yields than the unprotonated dyes. Transient absorption spectroscopy reveals four excited-state lifetimes (<1 ps, ∼3 ps, ∼13 ps, and ∼200 ps) exhibiting faster excited-state dynamics than observed in the unprotonated forms (for
1-3
: 0.7-1.5 ps, ∼3-4 ps, 20-40 ps, 20-300 min; for
4
: 0.7 ps, 4.8 ps, 17.8 ps, 40 ps, 8 min). Time-dependent density functional theory (TDDFT) elucidates the reason for the loss of isomerization in the protonated dyes, revealing a significant change in the lowest excited state potential energy nature and landscape upon protonation. Protonation impedes relaxation along the typical rotational and inversion isomerization axes, locking the dyes into a
trans
-configuration that rapidly decays back to the ground state.
Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/d4cp00242c</identifier><ispartof>Physical chemistry chemical physics : PCCP, 2024-04, Vol.26 (14), p.184-1813</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,777,781,27905,27906</link.rule.ids></links><search><creatorcontrib>Martin, Shea M</creatorcontrib><creatorcontrib>Hamburger, Robert C</creatorcontrib><creatorcontrib>Huang, Tao</creatorcontrib><creatorcontrib>Fredin, Lisa A</creatorcontrib><creatorcontrib>Young, Elizabeth R</creatorcontrib><title>Controlling excited-state dynamics protonation of naphthalene-based azo dyes</title><title>Physical chemistry chemical physics : PCCP</title><description>Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions. This work explores the impact of protonation on the photophysics of four naphthalene-based azo dyes. The p
K
a
value of the dyes increases proportionally with decreasing Hammett parameter of
p
-phenyl substituents from 8.1 (R = -H,
σ
= 0) to 10.6 (R = -NMe2,
σ
= -0.83) in acetonitrile. Protonation of the dyes shuts down the steady-state photoisomerization observed in the unprotonated moieties. Fluorescence measurements reveal a lower quantum yield with more electron-donating
p
-phenyl substituents, with overall lower fluorescence quantum yields than the unprotonated dyes. Transient absorption spectroscopy reveals four excited-state lifetimes (<1 ps, ∼3 ps, ∼13 ps, and ∼200 ps) exhibiting faster excited-state dynamics than observed in the unprotonated forms (for
1-3
: 0.7-1.5 ps, ∼3-4 ps, 20-40 ps, 20-300 min; for
4
: 0.7 ps, 4.8 ps, 17.8 ps, 40 ps, 8 min). Time-dependent density functional theory (TDDFT) elucidates the reason for the loss of isomerization in the protonated dyes, revealing a significant change in the lowest excited state potential energy nature and landscape upon protonation. Protonation impedes relaxation along the typical rotational and inversion isomerization axes, locking the dyes into a
trans
-configuration that rapidly decays back to the ground state.
Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions.</description><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFjr0OwiAYRYnRxN_F3YQXqELBaudG4-Do3nwCtRgKBBisT6-D0dHpnuSc4SK0pGRNCSs3kgtPSM5zMUATyguWlWTPh1_eFWM0jfFOCKFbyiboXDmbgjNG2xtWD6GTkllMkBSWvYVOi4h9cMlZSNpZ7BpswbepBaOsyq4QlcTwdO9axTkaNWCiWnx2hlbHw6U6ZSGK2gfdQejr30X2z78AVnJAJw</recordid><startdate>20240403</startdate><enddate>20240403</enddate><creator>Martin, Shea M</creator><creator>Hamburger, Robert C</creator><creator>Huang, Tao</creator><creator>Fredin, Lisa A</creator><creator>Young, Elizabeth R</creator><scope/></search><sort><creationdate>20240403</creationdate><title>Controlling excited-state dynamics protonation of naphthalene-based azo dyes</title><author>Martin, Shea M ; Hamburger, Robert C ; Huang, Tao ; Fredin, Lisa A ; Young, Elizabeth R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_d4cp00242c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Martin, Shea M</creatorcontrib><creatorcontrib>Hamburger, Robert C</creatorcontrib><creatorcontrib>Huang, Tao</creatorcontrib><creatorcontrib>Fredin, Lisa A</creatorcontrib><creatorcontrib>Young, Elizabeth R</creatorcontrib><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Martin, Shea M</au><au>Hamburger, Robert C</au><au>Huang, Tao</au><au>Fredin, Lisa A</au><au>Young, Elizabeth R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Controlling excited-state dynamics protonation of naphthalene-based azo dyes</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><date>2024-04-03</date><risdate>2024</risdate><volume>26</volume><issue>14</issue><spage>184</spage><epage>1813</epage><pages>184-1813</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions. This work explores the impact of protonation on the photophysics of four naphthalene-based azo dyes. The p
K
a
value of the dyes increases proportionally with decreasing Hammett parameter of
p
-phenyl substituents from 8.1 (R = -H,
σ
= 0) to 10.6 (R = -NMe2,
σ
= -0.83) in acetonitrile. Protonation of the dyes shuts down the steady-state photoisomerization observed in the unprotonated moieties. Fluorescence measurements reveal a lower quantum yield with more electron-donating
p
-phenyl substituents, with overall lower fluorescence quantum yields than the unprotonated dyes. Transient absorption spectroscopy reveals four excited-state lifetimes (<1 ps, ∼3 ps, ∼13 ps, and ∼200 ps) exhibiting faster excited-state dynamics than observed in the unprotonated forms (for
1-3
: 0.7-1.5 ps, ∼3-4 ps, 20-40 ps, 20-300 min; for
4
: 0.7 ps, 4.8 ps, 17.8 ps, 40 ps, 8 min). Time-dependent density functional theory (TDDFT) elucidates the reason for the loss of isomerization in the protonated dyes, revealing a significant change in the lowest excited state potential energy nature and landscape upon protonation. Protonation impedes relaxation along the typical rotational and inversion isomerization axes, locking the dyes into a
trans
-configuration that rapidly decays back to the ground state.
Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions.</abstract><doi>10.1039/d4cp00242c</doi><tpages>1</tpages></addata></record> |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| title | Controlling excited-state dynamics protonation of naphthalene-based azo dyes |
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