Evaluating the photophysical and photochemical characteristics of green-emitting cerium() mono-cyclooctatetraenide complexes
The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce( iii ) complexes: [(C 8 H 8 )Ce( μ -X)(THF) 2 ] 2 X = O 3 SCF 3 − ( 1 ), Cl − ( 2 ), were studied. In the course of these studies, a new polymorph of [(C 8 H 8 )Ce( μ -O 3 SCF 3 )(THF) 2 ] 2 ( 1 ) was d...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2023-05, Vol.52 (18), p.599-5917 |
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| creator | Pandey, Pragati Yang, Qiaomu Gau, Michael R Schelter, Eric J |
| description | The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied. In the course of these studies, a new polymorph of [(C
8
H
8
)Ce(
μ
-O
3
SCF
3
)(THF)
2
]
2
(
1
) was described. Photoluminescence (PL) studies of
1
and
2
showed characteristic excitation and emission bands in the visible region, with bright green light emission under light irradiation from states corresponding to the 5d → 4f transition. Complexes
1
and
2
exhibit relatively long lifetime of 205.4 ± 0.2 and 145.8 ± 0.4 ns respectively. And the quantum yields (
Φ
) for
1
and
2
are 0.180 and 0.068 respectively. Electrochemical studies were performed on complexes
1
and
2
with a reversible Ce(
iii
)/Ce(
iv
) redox couple recorded at
E
1/2
= −1.53 V
versus
the Fc/Fc
+
for
2
. Complex
1
shows an irreversible Ce(
iii
/
iv
) oxidation wave. Complexes
1
and
2
revealed strongly-reducing, estimated, excited state reduction potentials
of −3.31 and −4.02 V
versus
the Fc/Fc
+
respectively, with small Stokes shifts of 0.12 eV. With their associated relatively long lifetimes, small Stokes shifts and large, negative
values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.
The photophysical properties and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied. |
| doi_str_mv | 10.1039/d3dt00351e |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1039_D3DT00351E</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2802424176</sourcerecordid><originalsourceid>FETCH-LOGICAL-c364t-9041231b396071f43bbe480ac3d982a0c2a4cee417a359c0a51a914f5c76a83e3</originalsourceid><addsrcrecordid>eNpd0d9r1TAUB_AgipvTF9-V4l6mUM2v_sijbNdtMPBlPpdzT0_XjjapSSpe2B-_eDuvIAQSzvlwkvBl7K3gnwVX5kur2si5KgQ9Y8dCV1VupNLPD2dZHrFXIdxzLiUv5Et2pCpepiWO2cPmF4wLxMHeZbGnbO5ddHO_CwPCmIFt1wr2NO0r2IMHjOSHEAcMmeuyO09k89SP-ymYest09jGbnHU57nB0DiNEih7IDi1l6KZ5pN8UXrMXHYyB3jztJ-zHt83t-VV-8_3y-vzrTY6q1DE3XAupxFaZklei02q7JV1zQNWaWgJHCRqJtKhAFQY5FAKM0F2BVQm1InXCPqxzXXp0E3CIhD06awljI0ylRMUTOlvR7N3PhUJspiEgjSNYcktoZM2llumSMtHT_-i9W7xNX0hKCGGMLOqkPq0KvQvBU9fMfpjA7xrBmz_BNRfq4nYf3Cbh908jl-1E7YH-TSqBdyvwAQ_df8mrR0L6ni0</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2811199258</pqid></control><display><type>article</type><title>Evaluating the photophysical and photochemical characteristics of green-emitting cerium() mono-cyclooctatetraenide complexes</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Pandey, Pragati ; Yang, Qiaomu ; Gau, Michael R ; Schelter, Eric J</creator><creatorcontrib>Pandey, Pragati ; Yang, Qiaomu ; Gau, Michael R ; Schelter, Eric J</creatorcontrib><description>The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied. In the course of these studies, a new polymorph of [(C
8
H
8
)Ce(
μ
-O
3
SCF
3
)(THF)
2
]
2
(
1
) was described. Photoluminescence (PL) studies of
1
and
2
showed characteristic excitation and emission bands in the visible region, with bright green light emission under light irradiation from states corresponding to the 5d → 4f transition. Complexes
1
and
2
exhibit relatively long lifetime of 205.4 ± 0.2 and 145.8 ± 0.4 ns respectively. And the quantum yields (
Φ
) for
1
and
2
are 0.180 and 0.068 respectively. Electrochemical studies were performed on complexes
1
and
2
with a reversible Ce(
iii
)/Ce(
iv
) redox couple recorded at
E
1/2
= −1.53 V
versus
the Fc/Fc
+
for
2
. Complex
1
shows an irreversible Ce(
iii
/
iv
) oxidation wave. Complexes
1
and
2
revealed strongly-reducing, estimated, excited state reduction potentials
of −3.31 and −4.02 V
versus
the Fc/Fc
+
respectively, with small Stokes shifts of 0.12 eV. With their associated relatively long lifetimes, small Stokes shifts and large, negative
values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.
The photophysical properties and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d3dt00351e</identifier><identifier>PMID: 37067061</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Cerium ; Emission analysis ; Light emission ; Light irradiation ; Oxidation ; Photoluminescence ; State reduction</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2023-05, Vol.52 (18), p.599-5917</ispartof><rights>Copyright Royal Society of Chemistry 2023</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c364t-9041231b396071f43bbe480ac3d982a0c2a4cee417a359c0a51a914f5c76a83e3</citedby><cites>FETCH-LOGICAL-c364t-9041231b396071f43bbe480ac3d982a0c2a4cee417a359c0a51a914f5c76a83e3</cites><orcidid>0000-0002-4790-6980 ; 0000-0002-4231-1355 ; 0000-0003-0032-7364 ; 0000-0002-8143-6206 ; 0000000242311355 ; 0000000300327364 ; 0000000247906980 ; 0000000281436206</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37067061$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1973170$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Pandey, Pragati</creatorcontrib><creatorcontrib>Yang, Qiaomu</creatorcontrib><creatorcontrib>Gau, Michael R</creatorcontrib><creatorcontrib>Schelter, Eric J</creatorcontrib><title>Evaluating the photophysical and photochemical characteristics of green-emitting cerium() mono-cyclooctatetraenide complexes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied. In the course of these studies, a new polymorph of [(C
8
H
8
)Ce(
μ
-O
3
SCF
3
)(THF)
2
]
2
(
1
) was described. Photoluminescence (PL) studies of
1
and
2
showed characteristic excitation and emission bands in the visible region, with bright green light emission under light irradiation from states corresponding to the 5d → 4f transition. Complexes
1
and
2
exhibit relatively long lifetime of 205.4 ± 0.2 and 145.8 ± 0.4 ns respectively. And the quantum yields (
Φ
) for
1
and
2
are 0.180 and 0.068 respectively. Electrochemical studies were performed on complexes
1
and
2
with a reversible Ce(
iii
)/Ce(
iv
) redox couple recorded at
E
1/2
= −1.53 V
versus
the Fc/Fc
+
for
2
. Complex
1
shows an irreversible Ce(
iii
/
iv
) oxidation wave. Complexes
1
and
2
revealed strongly-reducing, estimated, excited state reduction potentials
of −3.31 and −4.02 V
versus
the Fc/Fc
+
respectively, with small Stokes shifts of 0.12 eV. With their associated relatively long lifetimes, small Stokes shifts and large, negative
values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.
The photophysical properties and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied.</description><subject>Cerium</subject><subject>Emission analysis</subject><subject>Light emission</subject><subject>Light irradiation</subject><subject>Oxidation</subject><subject>Photoluminescence</subject><subject>State reduction</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpd0d9r1TAUB_AgipvTF9-V4l6mUM2v_sijbNdtMPBlPpdzT0_XjjapSSpe2B-_eDuvIAQSzvlwkvBl7K3gnwVX5kur2si5KgQ9Y8dCV1VupNLPD2dZHrFXIdxzLiUv5Et2pCpepiWO2cPmF4wLxMHeZbGnbO5ddHO_CwPCmIFt1wr2NO0r2IMHjOSHEAcMmeuyO09k89SP-ymYest09jGbnHU57nB0DiNEih7IDi1l6KZ5pN8UXrMXHYyB3jztJ-zHt83t-VV-8_3y-vzrTY6q1DE3XAupxFaZklei02q7JV1zQNWaWgJHCRqJtKhAFQY5FAKM0F2BVQm1InXCPqxzXXp0E3CIhD06awljI0ylRMUTOlvR7N3PhUJspiEgjSNYcktoZM2llumSMtHT_-i9W7xNX0hKCGGMLOqkPq0KvQvBU9fMfpjA7xrBmz_BNRfq4nYf3Cbh908jl-1E7YH-TSqBdyvwAQ_df8mrR0L6ni0</recordid><startdate>20230509</startdate><enddate>20230509</enddate><creator>Pandey, Pragati</creator><creator>Yang, Qiaomu</creator><creator>Gau, Michael R</creator><creator>Schelter, Eric J</creator><general>Royal Society of Chemistry</general><general>Royal Society of Chemistry (RSC)</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-4790-6980</orcidid><orcidid>https://orcid.org/0000-0002-4231-1355</orcidid><orcidid>https://orcid.org/0000-0003-0032-7364</orcidid><orcidid>https://orcid.org/0000-0002-8143-6206</orcidid><orcidid>https://orcid.org/0000000242311355</orcidid><orcidid>https://orcid.org/0000000300327364</orcidid><orcidid>https://orcid.org/0000000247906980</orcidid><orcidid>https://orcid.org/0000000281436206</orcidid></search><sort><creationdate>20230509</creationdate><title>Evaluating the photophysical and photochemical characteristics of green-emitting cerium() mono-cyclooctatetraenide complexes</title><author>Pandey, Pragati ; Yang, Qiaomu ; Gau, Michael R ; Schelter, Eric J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c364t-9041231b396071f43bbe480ac3d982a0c2a4cee417a359c0a51a914f5c76a83e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Cerium</topic><topic>Emission analysis</topic><topic>Light emission</topic><topic>Light irradiation</topic><topic>Oxidation</topic><topic>Photoluminescence</topic><topic>State reduction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Pandey, Pragati</creatorcontrib><creatorcontrib>Yang, Qiaomu</creatorcontrib><creatorcontrib>Gau, Michael R</creatorcontrib><creatorcontrib>Schelter, Eric J</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Pandey, Pragati</au><au>Yang, Qiaomu</au><au>Gau, Michael R</au><au>Schelter, Eric J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Evaluating the photophysical and photochemical characteristics of green-emitting cerium() mono-cyclooctatetraenide complexes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2023-05-09</date><risdate>2023</risdate><volume>52</volume><issue>18</issue><spage>599</spage><epage>5917</epage><pages>599-5917</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The photophysical and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied. In the course of these studies, a new polymorph of [(C
8
H
8
)Ce(
μ
-O
3
SCF
3
)(THF)
2
]
2
(
1
) was described. Photoluminescence (PL) studies of
1
and
2
showed characteristic excitation and emission bands in the visible region, with bright green light emission under light irradiation from states corresponding to the 5d → 4f transition. Complexes
1
and
2
exhibit relatively long lifetime of 205.4 ± 0.2 and 145.8 ± 0.4 ns respectively. And the quantum yields (
Φ
) for
1
and
2
are 0.180 and 0.068 respectively. Electrochemical studies were performed on complexes
1
and
2
with a reversible Ce(
iii
)/Ce(
iv
) redox couple recorded at
E
1/2
= −1.53 V
versus
the Fc/Fc
+
for
2
. Complex
1
shows an irreversible Ce(
iii
/
iv
) oxidation wave. Complexes
1
and
2
revealed strongly-reducing, estimated, excited state reduction potentials
of −3.31 and −4.02 V
versus
the Fc/Fc
+
respectively, with small Stokes shifts of 0.12 eV. With their associated relatively long lifetimes, small Stokes shifts and large, negative
values, both complexes were evaluated as potential photosensitisers for halogen atom transfer (XAT) using a test reaction of the dehalogenation of benzyl chloride.
The photophysical properties and photochemical reactivity of the organometallic mono(cyclooctatetraenide)-Ce(
iii
) complexes: [(C
8
H
8
)Ce(
μ
-X)(THF)
2
]
2
X = O
3
SCF
3
−
(
1
), Cl
−
(
2
), were studied.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>37067061</pmid><doi>10.1039/d3dt00351e</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-4790-6980</orcidid><orcidid>https://orcid.org/0000-0002-4231-1355</orcidid><orcidid>https://orcid.org/0000-0003-0032-7364</orcidid><orcidid>https://orcid.org/0000-0002-8143-6206</orcidid><orcidid>https://orcid.org/0000000242311355</orcidid><orcidid>https://orcid.org/0000000300327364</orcidid><orcidid>https://orcid.org/0000000247906980</orcidid><orcidid>https://orcid.org/0000000281436206</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2023-05, Vol.52 (18), p.599-5917 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_crossref_primary_10_1039_D3DT00351E |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Cerium Emission analysis Light emission Light irradiation Oxidation Photoluminescence State reduction |
| title | Evaluating the photophysical and photochemical characteristics of green-emitting cerium() mono-cyclooctatetraenide complexes |
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