Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings
Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E...
Saved in:
| Published in: | Inorganic chemistry Vol. 54; no. 20; pp. 9790 - 9801 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
19.10.2015
|
| Subjects: | |
| ISSN: | 1520-510X |
| Online Access: | Get more information |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Abstract | Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E = 0.1(2) cm⁻¹ and D = 13.4(6) cm⁻¹, E = 0.3(6) cm⁻¹ for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the ⁶A₁ ground state. D was calculated from wave functions of the electronic multiplets spanned by the d⁵ configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX₆³⁻ complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e(λ)(X) (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed. |
|---|---|
| AbstractList | Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E = 0.1(2) cm⁻¹ and D = 13.4(6) cm⁻¹, E = 0.3(6) cm⁻¹ for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the ⁶A₁ ground state. D was calculated from wave functions of the electronic multiplets spanned by the d⁵ configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX₆³⁻ complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e(λ)(X) (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed. |
| Author | Neese, Frank Stavretis, Shelby E Hunter, Seth C Xue, Zi-Ling Atanasov, Mihail Podlesnyak, Andrey A |
| Author_xml | – sequence: 1 givenname: Shelby E surname: Stavretis fullname: Stavretis, Shelby E organization: Department of Chemistry, The University of Tennessee , Knoxville, Tennessee 37996, United States – sequence: 2 givenname: Mihail surname: Atanasov fullname: Atanasov, Mihail organization: Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences , 1113 Sofia, Bulgaria – sequence: 3 givenname: Andrey A surname: Podlesnyak fullname: Podlesnyak, Andrey A organization: Quantum Condensed Matter Division, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States – sequence: 4 givenname: Seth C surname: Hunter fullname: Hunter, Seth C organization: Department of Chemistry, The University of Tennessee , Knoxville, Tennessee 37996, United States – sequence: 5 givenname: Frank surname: Neese fullname: Neese, Frank organization: Max Planck Institute for Chemical Energy Conversion , Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany – sequence: 6 givenname: Zi-Ling surname: Xue fullname: Xue, Zi-Ling organization: Department of Chemistry, The University of Tennessee , Knoxville, Tennessee 37996, United States |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/26428688$$D View this record in MEDLINE/PubMed |
| BookMark | eNo10D1PwzAQBmALgSgt_ASQR5YU24k_OlYVpZXKh9QiIZbISS6tUWIX2xk68N9JRdENp5Oe9x1uiM6ts4DQLSVjShh90GUYG-v8ttxBO-YFoZzwM3RFOSMJp-RjgIYhfBFCJmkmLtGAiYwpodQV-nnWWwvRlHjjtQ0mGmcDNhYvvbP4zfn97uD7c6EbU0HAxQEvLTQ6HCMv0MUjW5c6RujZFmtb4WnRm2MTXseuMn3K1fgTvEvmBpoKr_eNibHX4Rpd1LoJcHPaI_Q-f9zMFsnq9Wk5m64SzVkWE1FwUaV8olhNZM1UpqAfKoHKukhpWmoFLJU6lVIpUWoJGROSTQQFTXldsBG6_-vde_fdQYh5a0IJTaMtuC7kVLI-QYhSPb070a5oocr33rTaH_L_l7FfLfJx4g |
| CitedBy_id | crossref_primary_10_3390_inorganics6010024 crossref_primary_10_1039_D5NJ01857A crossref_primary_10_1007_s12274_022_4467_3 crossref_primary_10_1021_acs_cgd_5c00110 crossref_primary_10_1038_s41467_018_04896_0 crossref_primary_10_1021_jacs_9b12797 crossref_primary_10_1002_chem_201704546 crossref_primary_10_1002_ejic_201801088 crossref_primary_10_1016_j_synthmet_2016_02_014 crossref_primary_10_1016_j_synthmet_2021_116696 crossref_primary_10_1039_D5NJ00184F crossref_primary_10_1021_acs_inorgchem_5c01776 crossref_primary_10_1002_chem_202102572 crossref_primary_10_1039_D5SC03103F crossref_primary_10_1039_D4SC05471G crossref_primary_10_1039_D5CC04404A crossref_primary_10_1007_s00723_020_01236_8 crossref_primary_10_1007_s00723_020_01239_5 crossref_primary_10_1002_chem_202003052 crossref_primary_10_1146_annurev_matsci_081420_042553 crossref_primary_10_1021_acs_inorgchem_5b02545 crossref_primary_10_1063_1_5055743 crossref_primary_10_1016_j_dyepig_2018_09_058 crossref_primary_10_1002_chem_202100705 crossref_primary_10_1002_ejic_201801076 crossref_primary_10_1021_acs_inorgchem_5c02691 crossref_primary_10_1002_chem_202103775 crossref_primary_10_7566_JPSJ_87_013702 crossref_primary_10_1002_chem_201903635 crossref_primary_10_1039_C8QI00701B crossref_primary_10_1002_adfm_202004744 crossref_primary_10_1016_j_jpcs_2023_111514 crossref_primary_10_1039_D4CY00999A crossref_primary_10_1016_j_poly_2020_114488 |
| ContentType | Journal Article |
| DBID | CGR CUY CVF ECM EIF NPM 7X8 |
| DOI | 10.1021/acs.inorgchem.5b01505 |
| DatabaseName | Medline MEDLINE MEDLINE (Ovid) MEDLINE MEDLINE PubMed MEDLINE - Academic |
| DatabaseTitle | MEDLINE Medline Complete MEDLINE with Full Text PubMed MEDLINE (Ovid) MEDLINE - Academic |
| DatabaseTitleList | MEDLINE MEDLINE - Academic |
| Database_xml | – sequence: 1 dbid: NPM name: PubMed url: http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database – sequence: 2 dbid: 7X8 name: MEDLINE - Academic url: https://search.proquest.com/medline sourceTypes: Aggregation Database |
| DeliveryMethod | no_fulltext_linktorsrc |
| Discipline | Chemistry |
| EISSN | 1520-510X |
| EndPage | 9801 |
| ExternalDocumentID | 26428688 |
| Genre | Research Support, U.S. Gov't, Non-P.H.S Research Support, Non-U.S. Gov't Journal Article |
| GroupedDBID | --- -DZ -~X .K2 4.4 53G 55A 5GY 5VS 7~N 85S AABXI ABBLG ABJNI ABLBI ABMVS ABPPZ ABQRX ABUCX ACGFS ACJ ACNCT ACS ADHLV AEESW AENEX AFEFF AGXLV AHGAQ ALMA_UNASSIGNED_HOLDINGS AQSVZ BAANH CGR CS3 CUPRZ CUY CVF D0L DU5 EBS ECM ED~ EIF EJD F5P GGK GNL IH2 IH9 IHE JG~ LG6 NPM ROL RXW TAE TN5 TWZ UI2 UKR UPT VF5 VG9 W1F WH7 XSW YZZ ~02 7X8 |
| ID | FETCH-LOGICAL-a524t-6b56d35982f07f2848e8e817e17fb313ca8e237a377886ca7e42672961ea15fb2 |
| IEDL.DBID | 7X8 |
| ISICitedReferencesCount | 57 |
| ISICitedReferencesURI | http://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestLinkType=CitingArticles&DestApp=WOS_CPL&KeyUT=000363224000018&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| IngestDate | Fri Jul 11 16:34:26 EDT 2025 Mon Jul 21 06:03:35 EDT 2025 |
| IsDoiOpenAccess | false |
| IsOpenAccess | true |
| IsPeerReviewed | true |
| IsScholarly | true |
| Issue | 20 |
| Language | English |
| LinkModel | DirectLink |
| MergedId | FETCHMERGED-LOGICAL-a524t-6b56d35982f07f2848e8e817e17fb313ca8e237a377886ca7e42672961ea15fb2 |
| Notes | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| OpenAccessLink | https://www.osti.gov/servlets/purl/1224166 |
| PMID | 26428688 |
| PQID | 1724260088 |
| PQPubID | 23479 |
| PageCount | 12 |
| ParticipantIDs | proquest_miscellaneous_1724260088 pubmed_primary_26428688 |
| PublicationCentury | 2000 |
| PublicationDate | 2015-10-19 |
| PublicationDateYYYYMMDD | 2015-10-19 |
| PublicationDate_xml | – month: 10 year: 2015 text: 2015-10-19 day: 19 |
| PublicationDecade | 2010 |
| PublicationPlace | United States |
| PublicationPlace_xml | – name: United States |
| PublicationTitle | Inorganic chemistry |
| PublicationTitleAlternate | Inorg Chem |
| PublicationYear | 2015 |
| SSID | ssj0009346 |
| Score | 2.4143648 |
| Snippet | Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined... |
| SourceID | proquest pubmed |
| SourceType | Aggregation Database Index Database |
| StartPage | 9790 |
| SubjectTerms | Iron - chemistry Magnetic Fields Metalloporphyrins - chemistry Molecular Conformation Neutrons Quantum Theory Scattering, Radiation |
| Title | Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings |
| URI | https://www.ncbi.nlm.nih.gov/pubmed/26428688 https://www.proquest.com/docview/1724260088 |
| Volume | 54 |
| WOSCitedRecordID | wos000363224000018&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| hasFullText | |
| inHoldings | 1 |
| isFullTextHit | |
| isPrint | |
| link | http://cvtisr.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwpV1bS8MwFA7eQF-8X-aNCL7GrematE8yhmN7sAxUGL6MpDkdezDV1gk--N89STt8EgQpFApNCV_SnO-cnHyHkGtQMgyzTDCuE8O6ETdMm9wwJ6XWjXRHK5P7YhMyTePJJBk3AbeqSatcrol-oTZF5mLkbTS0Xkw9jm9f35irGuV2V5sSGqtkPUQq41K65ORHLTwJu2J5aocHbZVVyGaLcoZwvNxgR5AMRb8zS29hBjv_7dsu2W64Je3Vk2GPrIDdJ5v9ZUm3A_J1r2bWnVqk3kTV2Vp0bumoLCwdFw7zEh-HSM4NVFR_0pEF5NeuSQoLFzanD5mX5ESTR5U1tKfxHfcl2qQk0iKnz1AWbOCS4-gDslyfW10dkqfB3WN_yJr6C0xFvPvOhI6E8Qp_eUfmaMdiwCuQEMhcI96ZioGHUoUS_WiRKQmIApJ1EYAKolzzI7JmCwsnhPJAi9C5J84XlxwSlWjZUejcGAFSQotcLZGdIiZu00JZKBbV9AfbFjmuh2f6WgtxTLlznkQcn_6h9RnZQq7jVVeD5Jys5_h3wwXZyD7e51V56ScO3tPx_TfyytFq |
| linkProvider | ProQuest |
| openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Magnetic+Transitions+in+Iron+Porphyrin+Halides+by+Inelastic+Neutron+Scattering+and+Ab+Initio+Studies+of+Zero-Field+Splittings&rft.jtitle=Inorganic+chemistry&rft.au=Stavretis%2C+Shelby+E&rft.au=Atanasov%2C+Mihail&rft.au=Podlesnyak%2C+Andrey+A&rft.au=Hunter%2C+Seth+C&rft.date=2015-10-19&rft.eissn=1520-510X&rft.volume=54&rft.issue=20&rft.spage=9790&rft_id=info:doi/10.1021%2Facs.inorgchem.5b01505&rft_id=info%3Apmid%2F26428688&rft_id=info%3Apmid%2F26428688&rft.externalDocID=26428688 |