Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand
The lanthanide complexes EuL 3 , GdL 3 , YbL 3 and LuL 3 of the N , N ′-bis(2-hydroxy-di-3,5- tert -butylphenyl)amine were prepared. The X-Ray crystal structures of GdL 3 and LuL 3 demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ) − . T...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2020-06, Vol.49 (24), p.8238-8246 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Mouchel Dit Leguerrier, D Barré, R Bryden, M Imbert, D Philouze, C Jarjayes, O Luneau, D Molloy, J. K Thomas, F |
| description | The lanthanide complexes
EuL
3
,
GdL
3
,
YbL
3
and
LuL
3
of the
N
,
N
′-bis(2-hydroxy-di-3,5-
tert
-butylphenyl)amine were prepared. The X-Ray crystal structures of
GdL
3
and
LuL
3
demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ)
−
. The complexes showed three oxidation events (
E
ox1
1/2
= 0.15-0.16 V,
E
1/2
2
= 0.51-55 V, and
E
1/2
3
= 0.75-0.78 V
vs.
Fc
+
/Fc)
via
cyclic voltammetry, corresponding to the successive oxidation of the aminophenolate moeities to iminosemiquinone species. The complexes
GdL
3
and
YbL
3
were characterized by EPR spectroscopy, allowing for the determination of the zero field splitting (ZFS) parameters in the first case. The monocations
(LnL
3
)
+
and monoanions
(LnL
3
)
−
were electrochemically generated (Ln = Eu, Gd, Yb, Lu), as well as the dications
YbL
3
2+
and
LuL
3
2+
. The spins are antiferromagnetically exchange coupled in the diradical species
LuL
3
2+
(|
D
| = 260 MHz,
E
= 0). All the complexes (incl. neutral) possess a strong absorption band in the NIR region (730-840 nm,
> 19 mM
−1
cm
−1
) corresponding to ligand-based transitions.
Three ligand molecules coordinate under their anionic diamagnetic form; the complexes (Gd, Eu, Yb, Lu) can undergo reversible oxidations, affording radical species, as demonstrated by spectro-electrochemistry. |
| doi_str_mv | 10.1039/d0dt01388a |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_hal_p</sourceid><recordid>TN_cdi_hal_primary_oai_HAL_hal_02916328v1</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2415728326</sourcerecordid><originalsourceid>FETCH-LOGICAL-c410t-25d1306fbeb52c77779d22ee0e91dd36c59ea7b85dcf6d3db19a9b210a924d093</originalsourceid><addsrcrecordid>eNp90U1PGzEQBuAVaqXSlEvvSEa9AGKpP7IfPkYJkEpRc2h6trz2LDHa2IvtDSD-fJ2mClIP-GLLejSamTfLvhJ8TTDj3zXWERNW1_IoOybjqso5ZeMPhzctP2WfQ3jAmFJc0OPs9Vf0g4qDlx2SVqPQg4reBeV6o5CxWwjR3MtonA3ItcgaC7lyzmtjZQTkQbtnJFU0W0CdtHEtrdGAlNv0HTxDQE8mrpFEvbEKPFpe_bxaoi6VtPpL9rGVXYCTf_co-317s5rO88Xy7sd0ssjVmOCY00IThsu2gaagqkqHa0oBMHCiNStVwUFWTV1o1Zaa6YZwyRtKsOR0rDFno-xiX3ctO9F7s5H-RThpxHyyELs_TDkpGa23JNnzve29exzS8GJjgoIujQZuCIKmlipCeLUr--0_-uAGb9MkO1VUtGa0TOpyr1TaavDQHjogWOwyEzM8W_3NbJLw2R77oA7uLVPR6zaZ0_cM-wOxGJ9p</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2415728326</pqid></control><display><type>article</type><title>Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Mouchel Dit Leguerrier, D ; Barré, R ; Bryden, M ; Imbert, D ; Philouze, C ; Jarjayes, O ; Luneau, D ; Molloy, J. K ; Thomas, F</creator><creatorcontrib>Mouchel Dit Leguerrier, D ; Barré, R ; Bryden, M ; Imbert, D ; Philouze, C ; Jarjayes, O ; Luneau, D ; Molloy, J. K ; Thomas, F</creatorcontrib><description>The lanthanide complexes
EuL
3
,
GdL
3
,
YbL
3
and
LuL
3
of the
N
,
N
′-bis(2-hydroxy-di-3,5-
tert
-butylphenyl)amine were prepared. The X-Ray crystal structures of
GdL
3
and
LuL
3
demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ)
−
. The complexes showed three oxidation events (
E
ox1
1/2
= 0.15-0.16 V,
E
1/2
2
= 0.51-55 V, and
E
1/2
3
= 0.75-0.78 V
vs.
Fc
+
/Fc)
via
cyclic voltammetry, corresponding to the successive oxidation of the aminophenolate moeities to iminosemiquinone species. The complexes
GdL
3
and
YbL
3
were characterized by EPR spectroscopy, allowing for the determination of the zero field splitting (ZFS) parameters in the first case. The monocations
(LnL
3
)
+
and monoanions
(LnL
3
)
−
were electrochemically generated (Ln = Eu, Gd, Yb, Lu), as well as the dications
YbL
3
2+
and
LuL
3
2+
. The spins are antiferromagnetically exchange coupled in the diradical species
LuL
3
2+
(|
D
| = 260 MHz,
E
= 0). All the complexes (incl. neutral) possess a strong absorption band in the NIR region (730-840 nm,
> 19 mM
−1
cm
−1
) corresponding to ligand-based transitions.
Three ligand molecules coordinate under their anionic diamagnetic form; the complexes (Gd, Eu, Yb, Lu) can undergo reversible oxidations, affording radical species, as demonstrated by spectro-electrochemistry.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d0dt01388a</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Absorption spectra ; Antiferromagnetism ; Chemical Sciences ; Coordination chemistry ; Cristallography ; Crystal structure ; Crystallography ; Diamagnetism ; Gadolinium ; Ligands ; Oxidation</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2020-06, Vol.49 (24), p.8238-8246</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c410t-25d1306fbeb52c77779d22ee0e91dd36c59ea7b85dcf6d3db19a9b210a924d093</citedby><cites>FETCH-LOGICAL-c410t-25d1306fbeb52c77779d22ee0e91dd36c59ea7b85dcf6d3db19a9b210a924d093</cites><orcidid>0000-0002-6977-5192 ; 0000-0003-3519-6632 ; 0000-0002-1831-7693 ; 0000-0003-0038-4916</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27903,27904</link.rule.ids><backlink>$$Uhttps://hal.science/hal-02916328$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Mouchel Dit Leguerrier, D</creatorcontrib><creatorcontrib>Barré, R</creatorcontrib><creatorcontrib>Bryden, M</creatorcontrib><creatorcontrib>Imbert, D</creatorcontrib><creatorcontrib>Philouze, C</creatorcontrib><creatorcontrib>Jarjayes, O</creatorcontrib><creatorcontrib>Luneau, D</creatorcontrib><creatorcontrib>Molloy, J. K</creatorcontrib><creatorcontrib>Thomas, F</creatorcontrib><title>Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>The lanthanide complexes
EuL
3
,
GdL
3
,
YbL
3
and
LuL
3
of the
N
,
N
′-bis(2-hydroxy-di-3,5-
tert
-butylphenyl)amine were prepared. The X-Ray crystal structures of
GdL
3
and
LuL
3
demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ)
−
. The complexes showed three oxidation events (
E
ox1
1/2
= 0.15-0.16 V,
E
1/2
2
= 0.51-55 V, and
E
1/2
3
= 0.75-0.78 V
vs.
Fc
+
/Fc)
via
cyclic voltammetry, corresponding to the successive oxidation of the aminophenolate moeities to iminosemiquinone species. The complexes
GdL
3
and
YbL
3
were characterized by EPR spectroscopy, allowing for the determination of the zero field splitting (ZFS) parameters in the first case. The monocations
(LnL
3
)
+
and monoanions
(LnL
3
)
−
were electrochemically generated (Ln = Eu, Gd, Yb, Lu), as well as the dications
YbL
3
2+
and
LuL
3
2+
. The spins are antiferromagnetically exchange coupled in the diradical species
LuL
3
2+
(|
D
| = 260 MHz,
E
= 0). All the complexes (incl. neutral) possess a strong absorption band in the NIR region (730-840 nm,
> 19 mM
−1
cm
−1
) corresponding to ligand-based transitions.
Three ligand molecules coordinate under their anionic diamagnetic form; the complexes (Gd, Eu, Yb, Lu) can undergo reversible oxidations, affording radical species, as demonstrated by spectro-electrochemistry.</description><subject>Absorption spectra</subject><subject>Antiferromagnetism</subject><subject>Chemical Sciences</subject><subject>Coordination chemistry</subject><subject>Cristallography</subject><subject>Crystal structure</subject><subject>Crystallography</subject><subject>Diamagnetism</subject><subject>Gadolinium</subject><subject>Ligands</subject><subject>Oxidation</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp90U1PGzEQBuAVaqXSlEvvSEa9AGKpP7IfPkYJkEpRc2h6trz2LDHa2IvtDSD-fJ2mClIP-GLLejSamTfLvhJ8TTDj3zXWERNW1_IoOybjqso5ZeMPhzctP2WfQ3jAmFJc0OPs9Vf0g4qDlx2SVqPQg4reBeV6o5CxWwjR3MtonA3ItcgaC7lyzmtjZQTkQbtnJFU0W0CdtHEtrdGAlNv0HTxDQE8mrpFEvbEKPFpe_bxaoi6VtPpL9rGVXYCTf_co-317s5rO88Xy7sd0ssjVmOCY00IThsu2gaagqkqHa0oBMHCiNStVwUFWTV1o1Zaa6YZwyRtKsOR0rDFno-xiX3ctO9F7s5H-RThpxHyyELs_TDkpGa23JNnzve29exzS8GJjgoIujQZuCIKmlipCeLUr--0_-uAGb9MkO1VUtGa0TOpyr1TaavDQHjogWOwyEzM8W_3NbJLw2R77oA7uLVPR6zaZ0_cM-wOxGJ9p</recordid><startdate>20200628</startdate><enddate>20200628</enddate><creator>Mouchel Dit Leguerrier, D</creator><creator>Barré, R</creator><creator>Bryden, M</creator><creator>Imbert, D</creator><creator>Philouze, C</creator><creator>Jarjayes, O</creator><creator>Luneau, D</creator><creator>Molloy, J. K</creator><creator>Thomas, F</creator><general>Royal Society of Chemistry</general><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>1XC</scope><scope>VOOES</scope><orcidid>https://orcid.org/0000-0002-6977-5192</orcidid><orcidid>https://orcid.org/0000-0003-3519-6632</orcidid><orcidid>https://orcid.org/0000-0002-1831-7693</orcidid><orcidid>https://orcid.org/0000-0003-0038-4916</orcidid></search><sort><creationdate>20200628</creationdate><title>Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand</title><author>Mouchel Dit Leguerrier, D ; Barré, R ; Bryden, M ; Imbert, D ; Philouze, C ; Jarjayes, O ; Luneau, D ; Molloy, J. K ; Thomas, F</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c410t-25d1306fbeb52c77779d22ee0e91dd36c59ea7b85dcf6d3db19a9b210a924d093</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Absorption spectra</topic><topic>Antiferromagnetism</topic><topic>Chemical Sciences</topic><topic>Coordination chemistry</topic><topic>Cristallography</topic><topic>Crystal structure</topic><topic>Crystallography</topic><topic>Diamagnetism</topic><topic>Gadolinium</topic><topic>Ligands</topic><topic>Oxidation</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mouchel Dit Leguerrier, D</creatorcontrib><creatorcontrib>Barré, R</creatorcontrib><creatorcontrib>Bryden, M</creatorcontrib><creatorcontrib>Imbert, D</creatorcontrib><creatorcontrib>Philouze, C</creatorcontrib><creatorcontrib>Jarjayes, O</creatorcontrib><creatorcontrib>Luneau, D</creatorcontrib><creatorcontrib>Molloy, J. K</creatorcontrib><creatorcontrib>Thomas, F</creatorcontrib><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>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mouchel Dit Leguerrier, D</au><au>Barré, R</au><au>Bryden, M</au><au>Imbert, D</au><au>Philouze, C</au><au>Jarjayes, O</au><au>Luneau, D</au><au>Molloy, J. K</au><au>Thomas, F</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2020-06-28</date><risdate>2020</risdate><volume>49</volume><issue>24</issue><spage>8238</spage><epage>8246</epage><pages>8238-8246</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The lanthanide complexes
EuL
3
,
GdL
3
,
YbL
3
and
LuL
3
of the
N
,
N
′-bis(2-hydroxy-di-3,5-
tert
-butylphenyl)amine were prepared. The X-Ray crystal structures of
GdL
3
and
LuL
3
demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ)
−
. The complexes showed three oxidation events (
E
ox1
1/2
= 0.15-0.16 V,
E
1/2
2
= 0.51-55 V, and
E
1/2
3
= 0.75-0.78 V
vs.
Fc
+
/Fc)
via
cyclic voltammetry, corresponding to the successive oxidation of the aminophenolate moeities to iminosemiquinone species. The complexes
GdL
3
and
YbL
3
were characterized by EPR spectroscopy, allowing for the determination of the zero field splitting (ZFS) parameters in the first case. The monocations
(LnL
3
)
+
and monoanions
(LnL
3
)
−
were electrochemically generated (Ln = Eu, Gd, Yb, Lu), as well as the dications
YbL
3
2+
and
LuL
3
2+
. The spins are antiferromagnetically exchange coupled in the diradical species
LuL
3
2+
(|
D
| = 260 MHz,
E
= 0). All the complexes (incl. neutral) possess a strong absorption band in the NIR region (730-840 nm,
> 19 mM
−1
cm
−1
) corresponding to ligand-based transitions.
Three ligand molecules coordinate under their anionic diamagnetic form; the complexes (Gd, Eu, Yb, Lu) can undergo reversible oxidations, affording radical species, as demonstrated by spectro-electrochemistry.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0dt01388a</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-6977-5192</orcidid><orcidid>https://orcid.org/0000-0003-3519-6632</orcidid><orcidid>https://orcid.org/0000-0002-1831-7693</orcidid><orcidid>https://orcid.org/0000-0003-0038-4916</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2020-06, Vol.49 (24), p.8238-8246 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_hal_primary_oai_HAL_hal_02916328v1 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Absorption spectra Antiferromagnetism Chemical Sciences Coordination chemistry Cristallography Crystal structure Crystallography Diamagnetism Gadolinium Ligands Oxidation |
| title | Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand |
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