Loading…
X-ray absorption and emission spectroscopy of NS Cu()/() complexes
This study investigates the influence of ligand charge on transition energies in a series of CuN 2 S 2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally...
Saved in:
Published in: | Dalton transactions : an international journal of inorganic chemistry 2024-05, Vol.53 (18), p.7828-7838 |
---|---|
Main Authors: | , , , , |
Format: | Article |
Language: | |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
cited_by | |
---|---|
cites | |
container_end_page | 7838 |
container_issue | 18 |
container_start_page | 7828 |
container_title | Dalton transactions : an international journal of inorganic chemistry |
container_volume | 53 |
creator | Geoghegan, Blaise L Bilyj, Jessica K Bernhardt, Paul V DeBeer, Serena Cutsail, George E |
description | This study investigates the influence of ligand charge on transition energies in a series of CuN
2
S
2
complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(
ii
) complexes [
Cu
II
(HL1)
] (HL1
2−
= dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [
Cu
II
(HL2)
] (HL2
2−
= dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(
iii
) complex [
Cu
III
(L2)
], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L2
3−
ligand stabilizes the Cu(
iii
) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(
iii
) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.
The competing influences of both oxidation state and ligand protonation state in Cu(
ii
) and Cu(
iii
) Schiff base complexes are explored through copper K-edge X-ray absorption and valence-to-core emission spectroscopies along with DFT calculations. |
doi_str_mv | 10.1039/d4dt00085d |
format | article |
fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_d4dt00085d</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>d4dt00085d</sourcerecordid><originalsourceid>FETCH-rsc_primary_d4dt00085d3</originalsourceid><addsrcrecordid>eNpjYBAyNNAzNDC21E8xSSkxMDCwME1hYuA0NDE317U0MjZhgbONzDgYuIqLswwMjIwMTI04GZwidIsSKxUSk4rziwpKMvPzFBLzUhRSczOLi0Gc4oLU5JKi_OLk_IJKhfw0Bb9gBedSDU19DU2F5PzcgpzUitRiHgbWtMSc4lReKM3NIOvmGuLsoVtUnBxfUJSZm1hUGY9wmDEheQDr_zqw</addsrcrecordid><sourcetype>Publisher</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>X-ray absorption and emission spectroscopy of NS Cu()/() complexes</title><source>Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list)</source><creator>Geoghegan, Blaise L ; Bilyj, Jessica K ; Bernhardt, Paul V ; DeBeer, Serena ; Cutsail, George E</creator><creatorcontrib>Geoghegan, Blaise L ; Bilyj, Jessica K ; Bernhardt, Paul V ; DeBeer, Serena ; Cutsail, George E</creatorcontrib><description>This study investigates the influence of ligand charge on transition energies in a series of CuN
2
S
2
complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(
ii
) complexes [
Cu
II
(HL1)
] (HL1
2−
= dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [
Cu
II
(HL2)
] (HL2
2−
= dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(
iii
) complex [
Cu
III
(L2)
], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L2
3−
ligand stabilizes the Cu(
iii
) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(
iii
) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.
The competing influences of both oxidation state and ligand protonation state in Cu(
ii
) and Cu(
iii
) Schiff base complexes are explored through copper K-edge X-ray absorption and valence-to-core emission spectroscopies along with DFT calculations.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d4dt00085d</identifier><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2024-05, Vol.53 (18), p.7828-7838</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>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Geoghegan, Blaise L</creatorcontrib><creatorcontrib>Bilyj, Jessica K</creatorcontrib><creatorcontrib>Bernhardt, Paul V</creatorcontrib><creatorcontrib>DeBeer, Serena</creatorcontrib><creatorcontrib>Cutsail, George E</creatorcontrib><title>X-ray absorption and emission spectroscopy of NS Cu()/() complexes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>This study investigates the influence of ligand charge on transition energies in a series of CuN
2
S
2
complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(
ii
) complexes [
Cu
II
(HL1)
] (HL1
2−
= dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [
Cu
II
(HL2)
] (HL2
2−
= dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(
iii
) complex [
Cu
III
(L2)
], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L2
3−
ligand stabilizes the Cu(
iii
) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(
iii
) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.
The competing influences of both oxidation state and ligand protonation state in Cu(
ii
) and Cu(
iii
) Schiff base complexes are explored through copper K-edge X-ray absorption and valence-to-core emission spectroscopies along with DFT calculations.</description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNpjYBAyNNAzNDC21E8xSSkxMDCwME1hYuA0NDE317U0MjZhgbONzDgYuIqLswwMjIwMTI04GZwidIsSKxUSk4rziwpKMvPzFBLzUhRSczOLi0Gc4oLU5JKi_OLk_IJKhfw0Bb9gBedSDU19DU2F5PzcgpzUitRiHgbWtMSc4lReKM3NIOvmGuLsoVtUnBxfUJSZm1hUGY9wmDEheQDr_zqw</recordid><startdate>20240507</startdate><enddate>20240507</enddate><creator>Geoghegan, Blaise L</creator><creator>Bilyj, Jessica K</creator><creator>Bernhardt, Paul V</creator><creator>DeBeer, Serena</creator><creator>Cutsail, George E</creator><scope/></search><sort><creationdate>20240507</creationdate><title>X-ray absorption and emission spectroscopy of NS Cu()/() complexes</title><author>Geoghegan, Blaise L ; Bilyj, Jessica K ; Bernhardt, Paul V ; DeBeer, Serena ; Cutsail, George E</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_d4dt00085d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Geoghegan, Blaise L</creatorcontrib><creatorcontrib>Bilyj, Jessica K</creatorcontrib><creatorcontrib>Bernhardt, Paul V</creatorcontrib><creatorcontrib>DeBeer, Serena</creatorcontrib><creatorcontrib>Cutsail, George E</creatorcontrib><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Geoghegan, Blaise L</au><au>Bilyj, Jessica K</au><au>Bernhardt, Paul V</au><au>DeBeer, Serena</au><au>Cutsail, George E</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>X-ray absorption and emission spectroscopy of NS Cu()/() complexes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2024-05-07</date><risdate>2024</risdate><volume>53</volume><issue>18</issue><spage>7828</spage><epage>7838</epage><pages>7828-7838</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>This study investigates the influence of ligand charge on transition energies in a series of CuN
2
S
2
complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(
ii
) complexes [
Cu
II
(HL1)
] (HL1
2−
= dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [
Cu
II
(HL2)
] (HL2
2−
= dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(
iii
) complex [
Cu
III
(L2)
], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L2
3−
ligand stabilizes the Cu(
iii
) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(
iii
) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.
The competing influences of both oxidation state and ligand protonation state in Cu(
ii
) and Cu(
iii
) Schiff base complexes are explored through copper K-edge X-ray absorption and valence-to-core emission spectroscopies along with DFT calculations.</abstract><doi>10.1039/d4dt00085d</doi><tpages>11</tpages></addata></record> |
fulltext | fulltext |
identifier | ISSN: 1477-9226 |
ispartof | Dalton transactions : an international journal of inorganic chemistry, 2024-05, Vol.53 (18), p.7828-7838 |
issn | 1477-9226 1477-9234 |
language | |
recordid | cdi_rsc_primary_d4dt00085d |
source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
title | X-ray absorption and emission spectroscopy of NS Cu()/() complexes |
url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-25T21%3A21%3A46IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-rsc&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=X-ray%20absorption%20and%20emission%20spectroscopy%20of%20NS%20Cu()/()%20complexes&rft.jtitle=Dalton%20transactions%20:%20an%20international%20journal%20of%20inorganic%20chemistry&rft.au=Geoghegan,%20Blaise%20L&rft.date=2024-05-07&rft.volume=53&rft.issue=18&rft.spage=7828&rft.epage=7838&rft.pages=7828-7838&rft.issn=1477-9226&rft.eissn=1477-9234&rft_id=info:doi/10.1039/d4dt00085d&rft_dat=%3Crsc%3Ed4dt00085d%3C/rsc%3E%3Cgrp_id%3Ecdi_FETCH-rsc_primary_d4dt00085d3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |