Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination
We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate dis...
Gespeichert in:
| Veröffentlicht in: | Journal of the American Chemical Society 2010-03, Vol.132 (11), p.3737-3750 |
|---|---|
| Hauptverfasser: | , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 3750 |
|---|---|
| container_issue | 11 |
| container_start_page | 3737 |
| container_title | Journal of the American Chemical Society |
| container_volume | 132 |
| creator | Hu, Chuanjiang Sulok, Corinne D Paulat, Florian Lehnert, Nicolai Twigg, Anna I Hendrich, Michael P Schulz, Charles E Scheidt, W. Robert |
| description | We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate distinctive differences between the two states. These include characteristic molecular structure differences, Mössbauer spectra, magnetic circular dichroism spectroscopy, and integer-spin EPR spectral distinctions. These distinctions are supported by DFT calculations. The two states are characterized by very different spatial properties of the doubly occupied orbital of the high-spin that are consonant with the physical properties. |
| doi_str_mv | 10.1021/ja907584x |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_2846462</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>733579414</sourcerecordid><originalsourceid>FETCH-LOGICAL-a404t-226d558629430421ff1e62752d643d6b85922e75e86d96e682a47c105fb6ce453</originalsourceid><addsrcrecordid>eNptkc1u1DAUhS1ERYfCghdA3iDoItR2bMdhgYSG_gRVolLL2vIkNxOPMvbUdlrKK_DSdTtlBBKrK_t899xrH4TeUPKREkaPVqYmlVD85zM0o4KRQlAmn6MZIYQVlZLlPnoZ4yofOVP0BdpnhNaMqnqGfn-bYsIGXwSfvPuEv9qYrFtONg654DQAvrr1-HiENgXvbIsvk0kQse_xib2BYu596KzLd_jMLoficmMdbjL6oWkO8YUPm-EuPOoR39o04GZtO_PLj3D00LNrt969Qnu9GSO8fqoH6MfJ8dX8rDj_ftrMv5wXhhOeCsZkJ4SSrOZlfhDtewqSVYJ1kpedXChRMwaVACW7WoJUzPCqpUT0C9kCF-UB-rz13UyLNXQtuBTMqDfBrk24095Y_a_i7KCX_kYzxSWXLBu8fzII_nqCmPTaxhbG0TjwU9RVWYqq5pRn8nBLtsHHGKDfTaFEP2Snd9ll9u3fa-3IP2Fl4N0WMG3UKz8Fl3_pP0b3c_WiDw</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>733579414</pqid></control><display><type>article</type><title>Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination</title><source>MEDLINE</source><source>ACS Journals: American Chemical Society Web Editions</source><creator>Hu, Chuanjiang ; Sulok, Corinne D ; Paulat, Florian ; Lehnert, Nicolai ; Twigg, Anna I ; Hendrich, Michael P ; Schulz, Charles E ; Scheidt, W. Robert</creator><creatorcontrib>Hu, Chuanjiang ; Sulok, Corinne D ; Paulat, Florian ; Lehnert, Nicolai ; Twigg, Anna I ; Hendrich, Michael P ; Schulz, Charles E ; Scheidt, W. Robert</creatorcontrib><description>We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate distinctive differences between the two states. These include characteristic molecular structure differences, Mössbauer spectra, magnetic circular dichroism spectroscopy, and integer-spin EPR spectral distinctions. These distinctions are supported by DFT calculations. The two states are characterized by very different spatial properties of the doubly occupied orbital of the high-spin that are consonant with the physical properties.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja907584x</identifier><identifier>PMID: 20192189</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Circular Dichroism ; Crystallography, X-Ray ; Electron Spin Resonance Spectroscopy ; Electrons ; Imidazoles - chemistry ; Iron - chemistry ; Magnetics ; Metalloporphyrins - chemistry ; Models, Molecular ; Molecular Conformation ; Protons ; Quantum Theory ; Spectroscopy, Mossbauer</subject><ispartof>Journal of the American Chemical Society, 2010-03, Vol.132 (11), p.3737-3750</ispartof><rights>Copyright © 2010 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a404t-226d558629430421ff1e62752d643d6b85922e75e86d96e682a47c105fb6ce453</citedby><cites>FETCH-LOGICAL-a404t-226d558629430421ff1e62752d643d6b85922e75e86d96e682a47c105fb6ce453</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja907584x$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja907584x$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/20192189$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Hu, Chuanjiang</creatorcontrib><creatorcontrib>Sulok, Corinne D</creatorcontrib><creatorcontrib>Paulat, Florian</creatorcontrib><creatorcontrib>Lehnert, Nicolai</creatorcontrib><creatorcontrib>Twigg, Anna I</creatorcontrib><creatorcontrib>Hendrich, Michael P</creatorcontrib><creatorcontrib>Schulz, Charles E</creatorcontrib><creatorcontrib>Scheidt, W. Robert</creatorcontrib><title>Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate distinctive differences between the two states. These include characteristic molecular structure differences, Mössbauer spectra, magnetic circular dichroism spectroscopy, and integer-spin EPR spectral distinctions. These distinctions are supported by DFT calculations. The two states are characterized by very different spatial properties of the doubly occupied orbital of the high-spin that are consonant with the physical properties.</description><subject>Circular Dichroism</subject><subject>Crystallography, X-Ray</subject><subject>Electron Spin Resonance Spectroscopy</subject><subject>Electrons</subject><subject>Imidazoles - chemistry</subject><subject>Iron - chemistry</subject><subject>Magnetics</subject><subject>Metalloporphyrins - chemistry</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Protons</subject><subject>Quantum Theory</subject><subject>Spectroscopy, Mossbauer</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkc1u1DAUhS1ERYfCghdA3iDoItR2bMdhgYSG_gRVolLL2vIkNxOPMvbUdlrKK_DSdTtlBBKrK_t899xrH4TeUPKREkaPVqYmlVD85zM0o4KRQlAmn6MZIYQVlZLlPnoZ4yofOVP0BdpnhNaMqnqGfn-bYsIGXwSfvPuEv9qYrFtONg654DQAvrr1-HiENgXvbIsvk0kQse_xib2BYu596KzLd_jMLoficmMdbjL6oWkO8YUPm-EuPOoR39o04GZtO_PLj3D00LNrt969Qnu9GSO8fqoH6MfJ8dX8rDj_ftrMv5wXhhOeCsZkJ4SSrOZlfhDtewqSVYJ1kpedXChRMwaVACW7WoJUzPCqpUT0C9kCF-UB-rz13UyLNXQtuBTMqDfBrk24095Y_a_i7KCX_kYzxSWXLBu8fzII_nqCmPTaxhbG0TjwU9RVWYqq5pRn8nBLtsHHGKDfTaFEP2Snd9ll9u3fa-3IP2Fl4N0WMG3UKz8Fl3_pP0b3c_WiDw</recordid><startdate>20100324</startdate><enddate>20100324</enddate><creator>Hu, Chuanjiang</creator><creator>Sulok, Corinne D</creator><creator>Paulat, Florian</creator><creator>Lehnert, Nicolai</creator><creator>Twigg, Anna I</creator><creator>Hendrich, Michael P</creator><creator>Schulz, Charles E</creator><creator>Scheidt, W. Robert</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>5PM</scope></search><sort><creationdate>20100324</creationdate><title>Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination</title><author>Hu, Chuanjiang ; Sulok, Corinne D ; Paulat, Florian ; Lehnert, Nicolai ; Twigg, Anna I ; Hendrich, Michael P ; Schulz, Charles E ; Scheidt, W. Robert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a404t-226d558629430421ff1e62752d643d6b85922e75e86d96e682a47c105fb6ce453</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Circular Dichroism</topic><topic>Crystallography, X-Ray</topic><topic>Electron Spin Resonance Spectroscopy</topic><topic>Electrons</topic><topic>Imidazoles - chemistry</topic><topic>Iron - chemistry</topic><topic>Magnetics</topic><topic>Metalloporphyrins - chemistry</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Protons</topic><topic>Quantum Theory</topic><topic>Spectroscopy, Mossbauer</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hu, Chuanjiang</creatorcontrib><creatorcontrib>Sulok, Corinne D</creatorcontrib><creatorcontrib>Paulat, Florian</creatorcontrib><creatorcontrib>Lehnert, Nicolai</creatorcontrib><creatorcontrib>Twigg, Anna I</creatorcontrib><creatorcontrib>Hendrich, Michael P</creatorcontrib><creatorcontrib>Schulz, Charles E</creatorcontrib><creatorcontrib>Scheidt, W. Robert</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hu, Chuanjiang</au><au>Sulok, Corinne D</au><au>Paulat, Florian</au><au>Lehnert, Nicolai</au><au>Twigg, Anna I</au><au>Hendrich, Michael P</au><au>Schulz, Charles E</au><au>Scheidt, W. Robert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2010-03-24</date><risdate>2010</risdate><volume>132</volume><issue>11</issue><spage>3737</spage><epage>3750</epage><pages>3737-3750</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate distinctive differences between the two states. These include characteristic molecular structure differences, Mössbauer spectra, magnetic circular dichroism spectroscopy, and integer-spin EPR spectral distinctions. These distinctions are supported by DFT calculations. The two states are characterized by very different spatial properties of the doubly occupied orbital of the high-spin that are consonant with the physical properties.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>20192189</pmid><doi>10.1021/ja907584x</doi><tpages>14</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2010-03, Vol.132 (11), p.3737-3750 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_2846462 |
| source | MEDLINE; ACS Journals: American Chemical Society Web Editions |
| subjects | Circular Dichroism Crystallography, X-Ray Electron Spin Resonance Spectroscopy Electrons Imidazoles - chemistry Iron - chemistry Magnetics Metalloporphyrins - chemistry Models, Molecular Molecular Conformation Protons Quantum Theory Spectroscopy, Mossbauer |
| title | Just a Proton: Distinguishing the Two Electronic States of Five-Coordinate High-Spin Iron(II) Porphyrinates with Imidazole/ate Coordination |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-04T18%3A25%3A05IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Just%20a%20Proton:%20Distinguishing%20the%20Two%20Electronic%20States%20of%20Five-Coordinate%20High-Spin%20Iron(II)%20Porphyrinates%20with%20Imidazole/ate%20Coordination&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Hu,%20Chuanjiang&rft.date=2010-03-24&rft.volume=132&rft.issue=11&rft.spage=3737&rft.epage=3750&rft.pages=3737-3750&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/ja907584x&rft_dat=%3Cproquest_pubme%3E733579414%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=733579414&rft_id=info:pmid/20192189&rfr_iscdi=true |