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Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag ions
H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic vol...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2019-01, Vol.48 (2), p.535-546 |
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| Main Authors: | , , , , , , |
| Format: | Article |
| Language: | English |
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| cites | cdi_FETCH-LOGICAL-c403t-ad142f5dea76bab9d92f91c1e58b46a72c02a0ea522c81041ff2e1a6c69105633 |
| container_end_page | 546 |
| container_issue | 2 |
| container_start_page | 535 |
| container_title | Dalton transactions : an international journal of inorganic chemistry |
| container_volume | 48 |
| creator | Tadokoro, Makoto Isogai, Kazuo Harada, Shohei Kouchi, Takaya Yamane, Takeshi Sugaya, Tomoaki Kamebuchi, Hajime |
| description | H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic voltammetry measurements, newly prepared [Re
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
2
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
3
) existing as H-bonded dimers in a CH
2
Cl
2
solution showed a four-step and four-electron transfer containing two mixed-valency states of Re
II
Re
III
and Re
III
Re
IV
, and Os
II
Os
III
and Os
III
Os
VI
, respectively. Furthermore, [Re
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
4
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
5
), bridged by two Ag
+
ions instead of two H-bonding protons, were prepared, and their electrochemical behaviours changed to a two-step and four-electron transfer. It is clear that the H-bonded complex dimers
2
and
3
, connected by an LBHB, can be electrochemically stabilized into unique pairs of mixed-valency states by PCET, and the H-bonding proton transfer also controls the electrochemical redox behaviour.
H-Bonded metal complex dimers with reversible redox behavior connected by an LBHB can provide a unique mixed-valency state. However, the metal complexes substituted two H-bonding protons to two Ag
+
ions electrochemically have no mixed-valency state. |
| doi_str_mv | 10.1039/c8dt03962c |
| format | article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmed_primary_30525138</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2162444040</sourcerecordid><originalsourceid>FETCH-LOGICAL-c403t-ad142f5dea76bab9d92f91c1e58b46a72c02a0ea522c81041ff2e1a6c69105633</originalsourceid><addsrcrecordid>eNpdkc1LxDAUxIMofqxevCsBLyJUkzTJtkdZP0Hwsp5LmrxqpG3WJF3di3-70V1X8DQD82N4j0HokJJzSvLyQhcmJpVMb6BdysfjrGQ531x7JnfQXgivhDBGBNtGO3kSQfNiF31ez62BXgN2DZ55F12faTfMWjC4sx9gsrlqU77A9QJDCzp6p1-gs1q1uIYXNbfOY9fj6FUfbLTJdhBTqF2XWj6wsR34gGtvzXMqTTXx3eHLZ5zQsI-2GtUGOFjpCD3dXE8nd9nD4-395PIh05zkMVOGctYIA2osa1WXpmRNSTUFUdRcqjHThCkCSjCmC0o4bRoGVEktS0qEzPMROl32phffBgix6mzQ0LaqBzeEilEhqCCS0YSe_ENf3eD7dF2iJOOck3TTCJ0tKe1dCB6aauZtp_yioqT6XqWaFFfTn1UmCT5eVQ51B2aN_s6QgKMl4INep3-z5l9lRpKZ</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2162444040</pqid></control><display><type>article</type><title>Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag ions</title><source>Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list)</source><creator>Tadokoro, Makoto ; Isogai, Kazuo ; Harada, Shohei ; Kouchi, Takaya ; Yamane, Takeshi ; Sugaya, Tomoaki ; Kamebuchi, Hajime</creator><creatorcontrib>Tadokoro, Makoto ; Isogai, Kazuo ; Harada, Shohei ; Kouchi, Takaya ; Yamane, Takeshi ; Sugaya, Tomoaki ; Kamebuchi, Hajime</creatorcontrib><description>H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic voltammetry measurements, newly prepared [Re
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
2
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
3
) existing as H-bonded dimers in a CH
2
Cl
2
solution showed a four-step and four-electron transfer containing two mixed-valency states of Re
II
Re
III
and Re
III
Re
IV
, and Os
II
Os
III
and Os
III
Os
VI
, respectively. Furthermore, [Re
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
4
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
5
), bridged by two Ag
+
ions instead of two H-bonding protons, were prepared, and their electrochemical behaviours changed to a two-step and four-electron transfer. It is clear that the H-bonded complex dimers
2
and
3
, connected by an LBHB, can be electrochemically stabilized into unique pairs of mixed-valency states by PCET, and the H-bonding proton transfer also controls the electrochemical redox behaviour.
H-Bonded metal complex dimers with reversible redox behavior connected by an LBHB can provide a unique mixed-valency state. However, the metal complexes substituted two H-bonding protons to two Ag
+
ions electrochemically have no mixed-valency state.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c8dt03962c</identifier><identifier>PMID: 30525138</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Coordination compounds ; Crystallography ; Dichloromethane ; Dimers ; Electrochemical analysis ; Electron transfer ; Electrons ; Hydrogen bonds ; Protons ; Silver ; Transition metal compounds</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2019-01, Vol.48 (2), p.535-546</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c403t-ad142f5dea76bab9d92f91c1e58b46a72c02a0ea522c81041ff2e1a6c69105633</citedby><cites>FETCH-LOGICAL-c403t-ad142f5dea76bab9d92f91c1e58b46a72c02a0ea522c81041ff2e1a6c69105633</cites><orcidid>0000-0002-6290-6700 ; 0000-0003-2266-6412 ; 0000-0002-0049-7606</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30525138$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tadokoro, Makoto</creatorcontrib><creatorcontrib>Isogai, Kazuo</creatorcontrib><creatorcontrib>Harada, Shohei</creatorcontrib><creatorcontrib>Kouchi, Takaya</creatorcontrib><creatorcontrib>Yamane, Takeshi</creatorcontrib><creatorcontrib>Sugaya, Tomoaki</creatorcontrib><creatorcontrib>Kamebuchi, Hajime</creatorcontrib><title>Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag ions</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic voltammetry measurements, newly prepared [Re
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
2
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
3
) existing as H-bonded dimers in a CH
2
Cl
2
solution showed a four-step and four-electron transfer containing two mixed-valency states of Re
II
Re
III
and Re
III
Re
IV
, and Os
II
Os
III
and Os
III
Os
VI
, respectively. Furthermore, [Re
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
4
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
5
), bridged by two Ag
+
ions instead of two H-bonding protons, were prepared, and their electrochemical behaviours changed to a two-step and four-electron transfer. It is clear that the H-bonded complex dimers
2
and
3
, connected by an LBHB, can be electrochemically stabilized into unique pairs of mixed-valency states by PCET, and the H-bonding proton transfer also controls the electrochemical redox behaviour.
H-Bonded metal complex dimers with reversible redox behavior connected by an LBHB can provide a unique mixed-valency state. However, the metal complexes substituted two H-bonding protons to two Ag
+
ions electrochemically have no mixed-valency state.</description><subject>Coordination compounds</subject><subject>Crystallography</subject><subject>Dichloromethane</subject><subject>Dimers</subject><subject>Electrochemical analysis</subject><subject>Electron transfer</subject><subject>Electrons</subject><subject>Hydrogen bonds</subject><subject>Protons</subject><subject>Silver</subject><subject>Transition metal compounds</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpdkc1LxDAUxIMofqxevCsBLyJUkzTJtkdZP0Hwsp5LmrxqpG3WJF3di3-70V1X8DQD82N4j0HokJJzSvLyQhcmJpVMb6BdysfjrGQ531x7JnfQXgivhDBGBNtGO3kSQfNiF31ez62BXgN2DZ55F12faTfMWjC4sx9gsrlqU77A9QJDCzp6p1-gs1q1uIYXNbfOY9fj6FUfbLTJdhBTqF2XWj6wsR34gGtvzXMqTTXx3eHLZ5zQsI-2GtUGOFjpCD3dXE8nd9nD4-395PIh05zkMVOGctYIA2osa1WXpmRNSTUFUdRcqjHThCkCSjCmC0o4bRoGVEktS0qEzPMROl32phffBgix6mzQ0LaqBzeEilEhqCCS0YSe_ENf3eD7dF2iJOOck3TTCJ0tKe1dCB6aauZtp_yioqT6XqWaFFfTn1UmCT5eVQ51B2aN_s6QgKMl4INep3-z5l9lRpKZ</recordid><startdate>20190102</startdate><enddate>20190102</enddate><creator>Tadokoro, Makoto</creator><creator>Isogai, Kazuo</creator><creator>Harada, Shohei</creator><creator>Kouchi, Takaya</creator><creator>Yamane, Takeshi</creator><creator>Sugaya, Tomoaki</creator><creator>Kamebuchi, Hajime</creator><general>Royal Society of Chemistry</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><orcidid>https://orcid.org/0000-0002-6290-6700</orcidid><orcidid>https://orcid.org/0000-0003-2266-6412</orcidid><orcidid>https://orcid.org/0000-0002-0049-7606</orcidid></search><sort><creationdate>20190102</creationdate><title>Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag ions</title><author>Tadokoro, Makoto ; Isogai, Kazuo ; Harada, Shohei ; Kouchi, Takaya ; Yamane, Takeshi ; Sugaya, Tomoaki ; Kamebuchi, Hajime</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c403t-ad142f5dea76bab9d92f91c1e58b46a72c02a0ea522c81041ff2e1a6c69105633</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Coordination compounds</topic><topic>Crystallography</topic><topic>Dichloromethane</topic><topic>Dimers</topic><topic>Electrochemical analysis</topic><topic>Electron transfer</topic><topic>Electrons</topic><topic>Hydrogen bonds</topic><topic>Protons</topic><topic>Silver</topic><topic>Transition metal compounds</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tadokoro, Makoto</creatorcontrib><creatorcontrib>Isogai, Kazuo</creatorcontrib><creatorcontrib>Harada, Shohei</creatorcontrib><creatorcontrib>Kouchi, Takaya</creatorcontrib><creatorcontrib>Yamane, Takeshi</creatorcontrib><creatorcontrib>Sugaya, Tomoaki</creatorcontrib><creatorcontrib>Kamebuchi, Hajime</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><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tadokoro, Makoto</au><au>Isogai, Kazuo</au><au>Harada, Shohei</au><au>Kouchi, Takaya</au><au>Yamane, Takeshi</au><au>Sugaya, Tomoaki</au><au>Kamebuchi, Hajime</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag ions</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2019-01-02</date><risdate>2019</risdate><volume>48</volume><issue>2</issue><spage>535</spage><epage>546</epage><pages>535-546</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic voltammetry measurements, newly prepared [Re
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
2
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Hbim)]
2
(
3
) existing as H-bonded dimers in a CH
2
Cl
2
solution showed a four-step and four-electron transfer containing two mixed-valency states of Re
II
Re
III
and Re
III
Re
IV
, and Os
II
Os
III
and Os
III
Os
VI
, respectively. Furthermore, [Re
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
4
) and [Os
III
Cl
2
(P
n
Pr
3
)
2
(Agbim)]
2
(
5
), bridged by two Ag
+
ions instead of two H-bonding protons, were prepared, and their electrochemical behaviours changed to a two-step and four-electron transfer. It is clear that the H-bonded complex dimers
2
and
3
, connected by an LBHB, can be electrochemically stabilized into unique pairs of mixed-valency states by PCET, and the H-bonding proton transfer also controls the electrochemical redox behaviour.
H-Bonded metal complex dimers with reversible redox behavior connected by an LBHB can provide a unique mixed-valency state. However, the metal complexes substituted two H-bonding protons to two Ag
+
ions electrochemically have no mixed-valency state.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>30525138</pmid><doi>10.1039/c8dt03962c</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-6290-6700</orcidid><orcidid>https://orcid.org/0000-0003-2266-6412</orcidid><orcidid>https://orcid.org/0000-0002-0049-7606</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2019-01, Vol.48 (2), p.535-546 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_pubmed_primary_30525138 |
| source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
| subjects | Coordination compounds Crystallography Dichloromethane Dimers Electrochemical analysis Electron transfer Electrons Hydrogen bonds Protons Silver Transition metal compounds |
| title | Evidence of proton-coupled mixed-valency by electrochemical behavior on transition metal complex dimers bridged by two Ag ions |
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