{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,31]],"date-time":"2026-08-31T13:53:00Z","timestamp":1788184380377,"version":"build-2803163510"},"reference-count":28,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2023,4,11]],"date-time":"2023-04-11T00:00:00Z","timestamp":1681171200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["21-73-10126"],"award-info":[{"award-number":["21-73-10126"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>The geometry and electronic structures of iron(II) complexes with porphyrin (FeP) and tetrabenzoporphyrin (FeTBP) in ground and low-lying excited electronic states are determined by DFT (PBE0\/def2-TZVP) calculations and the complete active space self-consistent field (CASSCF) method, followed by the multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2) approach to determine the dynamic electron correlation. The minima on the potential energy surfaces (PESs) of the ground (3A2g) and low-lying, high-spin (5A1g) electronic states correspond to the planar structures of FeP and FeTBP with D4h symmetry. According to the results of the MCQDPT2 calculations, the wave functions of the 3A2g and 5A1g electronic states are single determinant. The electronic absorption (UV\u2013Vis) spectra of FeP and FeTBP are simulated within the framework of the simplified time-dependent density functional theory (sTDDFT) approach with the use of the long-range corrected CAM-B3LYP function. The most intensive bands of the UV\u2013Vis spectra of FeP and FeTBP occur in the Soret near-UV region of 370\u2013390 nm.<\/jats:p>","DOI":"10.3390\/ijms24087070","type":"journal-article","created":{"date-parts":[[2023,4,12]],"date-time":"2023-04-12T02:57:08Z","timestamp":1681268228000},"page":"7070","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Iron(II) Complexes with Porphyrin and Tetrabenzoporphyrin: CASSCF\/MCQDPT2 Study of the Electronic Structures and UV\u2013Vis Spectra by sTD-DFT"],"prefix":"10.3390","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7788-7231","authenticated-orcid":false,"given":"Alexey V.","family":"Eroshin","sequence":"first","affiliation":[{"name":"Research Institute of Chemistry of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and Technology, Sheremetievskiy Av. 7, 153000 Ivanovo, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8716-5427","authenticated-orcid":false,"given":"Andrey I.","family":"Koptyaev","sequence":"additional","affiliation":[{"name":"Research Institute of Chemistry of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and Technology, Sheremetievskiy Av. 7, 153000 Ivanovo, Russia"},{"name":"Institute for Physics of Microstructures RAS, GSP-105, 603950 Nizhny Novgorod, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6974-6327","authenticated-orcid":false,"given":"Arseniy A.","family":"Otlyotov","sequence":"additional","affiliation":[{"name":"N.N. Semenov Federal Research Center for Chemical Physics RAS, Kosygina Street 4, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yury","family":"Minenkov","sequence":"additional","affiliation":[{"name":"N.N. Semenov Federal Research Center for Chemical Physics RAS, Kosygina Street 4, 119991 Moscow, Russia"},{"name":"Joint Institute for High Temperatures, Russian Academy of Sciences, 13-2 Izhorskaya Street, 125412 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuriy A.","family":"Zhabanov","sequence":"additional","affiliation":[{"name":"Research Institute of Chemistry of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and Technology, Sheremetievskiy Av. 7, 153000 Ivanovo, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"450","DOI":"10.1246\/bcsj.45.450","article-title":"Electronic Spectra and Electronic Structure of Iron(II) Tetraphenylporphins","volume":"45","author":"Kobayashi","year":"1972","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2677","DOI":"10.1016\/0277-5387(95)00563-3","article-title":"A New Method of Preparation of Iron(II) Porphyrin Complexes\u2014Isolation and Characterization of Amine Complexes of Ferrous Porphyrin","volume":"15","author":"Xinhua","year":"1996","journal-title":"Polyhedron"},{"key":"ref_3","first-page":"224","article-title":"A Heme-like, Water-Soluble Iron (II) Porphyrin: Thermal and Photoinduced Properties, Evidence for Sitting-atop Structure","volume":"2","year":"2005","journal-title":"Chem. Commun."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Barona-Casta\u00f1o, J., Carmona-Vargas, C., Brocksom, T., and de Oliveira, K. (2016). Porphyrins as Catalysts in Scalable Organic Reactions. Molecules, 21.","DOI":"10.3390\/molecules21030310"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"126","DOI":"10.1016\/j.jinorgbio.2015.06.005","article-title":"Iron(II) Porphyrins Induced Conversion of Nitrite into Nitric Oxide: A Computational Study","volume":"150","author":"Zhang","year":"2015","journal-title":"J. Inorg. Biochem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3895","DOI":"10.1021\/acscatal.9b00529","article-title":"Reduction of CO2 to CO by an Iron Porphyrin Catalyst in the Presence of Oxygen","volume":"9","author":"Mondal","year":"2019","journal-title":"ACS Catal."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"100646","DOI":"10.1016\/j.rechem.2022.100646","article-title":"Green Light Harvester by Porphyrin Derivative Complexes: The Influence of Metal in Photovoltaic on Dye-Sensitized Solar Cells","volume":"4","author":"Darmokoesoemo","year":"2022","journal-title":"Results Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"14547","DOI":"10.1021\/acs.jpcc.9b03126","article-title":"Modifying the Magnetic Anisotropy of an Iron Porphyrin Molecule by an On-Surface Ring-Closure Reaction","volume":"123","author":"Arruda","year":"2019","journal-title":"J. Phys. Chem. C"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"4840","DOI":"10.1021\/nl402575c","article-title":"Change of the Magnetic Coupling of a Metal\u2013Organic Complex with the Substrate by a Stepwise Ligand Reaction","volume":"13","author":"Heinrich","year":"2013","journal-title":"Nano Lett."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1246\/cl.1983.163","article-title":"(TETRABENZPORPHINATO)IRON","volume":"12","author":"Kobayashi","year":"1983","journal-title":"Chem. Lett."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3297","DOI":"10.1039\/b508541a","article-title":"Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy","volume":"7","author":"Weigend","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1571","DOI":"10.1002\/(SICI)1096-987X(199610)17:13<1571::AID-JCC9>3.0.CO;2-P","article-title":"The Role of Databases in Support of Computational Chemistry Calculations","volume":"17","author":"Feller","year":"1996","journal-title":"J. Comput. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1045","DOI":"10.1021\/ci600510j","article-title":"Basis Set Exchange: A Community Database for Computational Sciences","volume":"47","author":"Schuchardt","year":"2007","journal-title":"J. Chem. Inf. Model."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4814","DOI":"10.1021\/acs.jcim.9b00725","article-title":"New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community","volume":"59","author":"Pritchard","year":"2019","journal-title":"J. Chem. Inf. Model."},{"key":"ref_15","unstructured":"Alex, A. (2021, April 15). Granovsky Firefly Version 8. Available online: http:\/\/classic.chem.msu.su\/gran\/gamess\/index.html."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1347","DOI":"10.1002\/jcc.540141112","article-title":"General Atomic and Molecular Electronic Structure System","volume":"14","author":"Schmidt","year":"1993","journal-title":"J. Comput. Chem."},{"key":"ref_17","unstructured":"Zhurko, G.A., and Zhurko, D.A. (2022, December 01). ChemCraft Version 1.6 (Build 312); Version 1.6 (Build 312) Ed. Available online: http:\/\/www.chemcraftprog.com\/index.html."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1016\/j.comptc.2014.02.023","article-title":"A Simplified Time-Dependent Density Functional Theory Approach for Electronic Ultraviolet and Circular Dichroism Spectra of Very Large Molecules","volume":"1040\u20131041","author":"Bannwarth","year":"2014","journal-title":"Comput. Theor. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1002\/wcms.81","article-title":"The ORCA Program System","volume":"2","author":"Neese","year":"2012","journal-title":"Wiley Interdiscip. Rev. Comput. Mol. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"e1606","DOI":"10.1002\/wcms.1606","article-title":"Software Update: The ORCA Program System\u2014Version 5.0","volume":"12","author":"Neese","year":"2022","journal-title":"WIREs Comput. Mol. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.cplett.2004.06.011","article-title":"A New Hybrid Exchange-Correlation Functional Using the Coulomb-Attenuating Method (CAM-B3LYP)","volume":"393","author":"Yanai","year":"2004","journal-title":"Chem. Phys. Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1057","DOI":"10.1039\/b515623h","article-title":"Accurate Coulomb-Fitting Basis Sets for H to Rn","volume":"8","author":"Weigend","year":"2006","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"98","DOI":"10.1016\/j.chemphys.2008.10.036","article-title":"Efficient, Approximate and Parallel Hartree-Fock and Hybrid DFT Calculations. A \u201cchain-of-Spheres\u201d Algorithm for the Hartree-Fock Exchange","volume":"356","author":"Neese","year":"2009","journal-title":"Chem. Phys."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A Multifunctional Wavefunction Analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1146","DOI":"10.1142\/S1088424620500285","article-title":"Peculiarities of Electronic Structure and Chemical Bonding in Iron and Cobalt Metal Complexes of Porphyrazine and Tetra(1,2,5-Thiadiazole)Porphyrazine","volume":"24","author":"Zhabanov","year":"2020","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_28","doi-asserted-by":"crossref","unstructured":"Eroshin, A.V., Otlyotov, A.A., Kuzmin, I.A., Stuzhin, P.A., and Zhabanov, Y.A. (2022). DFT Study of the Molecular and Electronic Structure of Metal-Free Tetrabenzoporphyrin and Its Metal Complexes with Zn, Cd, Al, Ga, In. Int. J. Mol. Sci., 23.","DOI":"10.3390\/ijms23020939"}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/24\/8\/7070\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:13:59Z","timestamp":1760123639000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/24\/8\/7070"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,4,11]]},"references-count":28,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2023,4]]}},"alternative-id":["ijms24087070"],"URL":"https:\/\/doi.org\/10.3390\/ijms24087070","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,4,11]]}}}