Unveiling ultrafast dynamics in bridged bimetallic complexes using optical and X-ray transient absorption spectroscopies
In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal-metal interactions in a bimetallic tetrapyridophe...
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| Veröffentlicht in: | Chemical science (Cambridge) 2022-02, Vol.13 (6), p.1715-1724 |
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| creator | Mara, Michael W Phelan, Brian T Xie, Zhu-Lin Kim, Tae Wu Hsu, Darren J Liu, Xiaolin Valentine, Andrew J. S Kim, Pyosang Li, Xiaosong Adachi, Shin-ichi Katayama, Tetsuo Mulfort, Karen L Chen, Lin X |
| description | In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal-metal interactions in a bimetallic tetrapyridophenazine-bridged Os(
ii
)/Cu(
i
) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(
ii
) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal-ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.
In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. |
| doi_str_mv | 10.1039/d1sc05034f |
| format | Article |
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ii
)/Cu(
i
) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(
ii
) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal-ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.
In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/d1sc05034f</identifier><identifier>PMID: 35282628</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Bimetals ; Charge transfer ; Chemistry ; Copper ; Coupling ; Excitation ; Ligands ; Osmium ; Photoexcitation ; Photosynthesis ; Transition metals ; X-ray spectroscopy</subject><ispartof>Chemical science (Cambridge), 2022-02, Vol.13 (6), p.1715-1724</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2022</rights><rights>This journal is © The Royal Society of Chemistry 2022 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c562t-880293aee4f4ab3e5c37699165cb2e06ce0e010aa471d1c4981cc6f559baa9933</citedby><cites>FETCH-LOGICAL-c562t-880293aee4f4ab3e5c37699165cb2e06ce0e010aa471d1c4981cc6f559baa9933</cites><orcidid>0000-0002-8450-6687 ; 0000-0003-3766-9368 ; 0000-0002-5849-0319 ; 0000-0002-1212-8760 ; 0000-0002-6370-0907 ; 0000-0002-3132-1179 ; 0000-0002-0353-7626 ; 0000-0002-1969-2831 ; 0000-0001-7341-6240 ; 0000000284506687 ; 0000000258490319 ; 0000000231321179 ; 0000000219692831 ; 0000000173416240 ; 0000000263700907 ; 0000000212128760 ; 0000000337669368 ; 0000000203537626</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC8827017/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC8827017/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27901,27902,53766,53768</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35282628$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1841596$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Mara, Michael W</creatorcontrib><creatorcontrib>Phelan, Brian T</creatorcontrib><creatorcontrib>Xie, Zhu-Lin</creatorcontrib><creatorcontrib>Kim, Tae Wu</creatorcontrib><creatorcontrib>Hsu, Darren J</creatorcontrib><creatorcontrib>Liu, Xiaolin</creatorcontrib><creatorcontrib>Valentine, Andrew J. S</creatorcontrib><creatorcontrib>Kim, Pyosang</creatorcontrib><creatorcontrib>Li, Xiaosong</creatorcontrib><creatorcontrib>Adachi, Shin-ichi</creatorcontrib><creatorcontrib>Katayama, Tetsuo</creatorcontrib><creatorcontrib>Mulfort, Karen L</creatorcontrib><creatorcontrib>Chen, Lin X</creatorcontrib><title>Unveiling ultrafast dynamics in bridged bimetallic complexes using optical and X-ray transient absorption spectroscopies</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal-metal interactions in a bimetallic tetrapyridophenazine-bridged Os(
ii
)/Cu(
i
) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(
ii
) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal-ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.
In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers.</description><subject>Bimetals</subject><subject>Charge transfer</subject><subject>Chemistry</subject><subject>Copper</subject><subject>Coupling</subject><subject>Excitation</subject><subject>Ligands</subject><subject>Osmium</subject><subject>Photoexcitation</subject><subject>Photosynthesis</subject><subject>Transition metals</subject><subject>X-ray spectroscopy</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNpdks1v1DAQxSMEolXphTvIgkuFFPBH7LUvldDSAlIlDlCJm-VMJltXiR3spOr-93jZsnz4Ykvv5-eZea6q54y-ZVSYdx3LQCUVTf-oOua0YbWSwjw-nDk9qk5zvqVlCcEkXz2tjoTkmiuuj6v763CHfvBhQ5ZhTq53eSbdNrjRQyY-kDb5boMdaf2IsxsGDwTiOA14j5kseXcxTrMHNxAXOvK9Tm5LilHIHsNMXJtjKnoMJE8Ic4oZ4uQxP6ue9G7IePqwn1TXlxff1p_qqy8fP6_fX9UgFZ9rrSk3wiE2feNagRLEShnDlISWI1WAFCmjzjUr1jFojGYAqpfStM4ZI8RJdb73nZZ2xA5KUckNdkp-dGlro_P2XyX4G7uJd1ZrvqJsVQxe7Q1inr3N4GeEG4ghlG4s0w2TRhXo7OGVFH8smGc7-gw4DC5gXLLlSmjTcMqagr7-D72NSwplBoXiyjBt6M7wzZ6CMrGcsD9UzKjdBW8_sK_rX8FfFvjl3z0e0N8xF-DFHkgZDuqfnyN-AswgtPM</recordid><startdate>20220209</startdate><enddate>20220209</enddate><creator>Mara, Michael W</creator><creator>Phelan, Brian T</creator><creator>Xie, Zhu-Lin</creator><creator>Kim, Tae Wu</creator><creator>Hsu, Darren J</creator><creator>Liu, Xiaolin</creator><creator>Valentine, Andrew J. 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S</au><au>Kim, Pyosang</au><au>Li, Xiaosong</au><au>Adachi, Shin-ichi</au><au>Katayama, Tetsuo</au><au>Mulfort, Karen L</au><au>Chen, Lin X</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Unveiling ultrafast dynamics in bridged bimetallic complexes using optical and X-ray transient absorption spectroscopies</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2022-02-09</date><risdate>2022</risdate><volume>13</volume><issue>6</issue><spage>1715</spage><epage>1724</epage><pages>1715-1724</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal-metal interactions in a bimetallic tetrapyridophenazine-bridged Os(
ii
)/Cu(
i
) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(
ii
) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal-ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.
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| source | DOAJ Directory of Open Access Journals; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; PubMed Central; PubMed Central Open Access |
| subjects | Bimetals Charge transfer Chemistry Copper Coupling Excitation Ligands Osmium Photoexcitation Photosynthesis Transition metals X-ray spectroscopy |
| title | Unveiling ultrafast dynamics in bridged bimetallic complexes using optical and X-ray transient absorption spectroscopies |
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