{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,18]],"date-time":"2026-03-18T23:39:48Z","timestamp":1773877188705,"version":"3.50.1"},"reference-count":37,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2024,6,24]],"date-time":"2024-06-24T00:00:00Z","timestamp":1719187200000},"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":["20-13-00359"],"award-info":[{"award-number":["20-13-00359"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Using quantum chemical calculation data obtained by the DFT method with the B3PW91\/TZVP and M062X\/def2TZVP theory levels, the possibility of the existence of four Be(II) coordination compounds, each of which contains in the inner coordination sphere and the double deprotonated forms of subporphyrazine (H2SP), mono[benzo]subporphyrazine (H2MBSP), di[benzo]subporphyrazine (H2DBSP), and tri[benzo]subporphyrazine (subphthalocyanine) (H2TBSP) with a ratio Be(II) ion\/ligand = 1:1, were examined Selected geometric parameters of the molecular structures of these (666)macrotricyclic complexes with closed contours are given; it was noted that BeN3 chelate nodes have a trigonal\u2013pyramidal structure and exhibit a very significant (almost 30\u00b0) deviation from coplanarity; however, all three 6-membered metal-chelate and three 5-membered non-chelate rings in each of these compounds are practically planar and deviate from coplanarity by no more than 2.5\u00b0. The bond angles between two nitrogen atoms and a Be atom are equal to 60\u00b0 (in the [BeSP] and [BeTBSP]) or less by no more than 0.5\u00b0 (in the [BeMBSP] and [BeDBSP]). The presence of annulated benzo groups has little effect on the parameters of the molecular structures of these complexes. Good agreement between the structural data obtained using the above two versions of the DFT method was noticed. NBO analysis data for these complexes are presented; it was noted that, according to both DFT methods used, the ground state of the each of complexes under study is a spin singlet. Standard thermodynamic parameters of formation (standard enthalpy \u0394fH0, entropy S0, and Gibbs free energy \u0394fG0) for the above-mentioned macrocyclic compounds were calculated.<\/jats:p>","DOI":"10.3390\/ijms25136897","type":"journal-article","created":{"date-parts":[[2024,6,24]],"date-time":"2024-06-24T08:42:03Z","timestamp":1719218523000},"page":"6897","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["First Examples of s-Metal Complexes with Subporphyrazine and Its Phenylene-Annulated Derivatives: DFT Calculations"],"prefix":"10.3390","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0073-3672","authenticated-orcid":false,"given":"Denis V.","family":"Chachkov","sequence":"first","affiliation":[{"name":"Kazan Department of Joint Supercomputer Center of Russian Academy of Sciences\u2013Branch of Federal Scientific Center \u201cScientific Research Institute for System Analysis of the RAS\u201d, Lobachevskii Street 2\/31, 420111 Kazan, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9136-5501","authenticated-orcid":false,"given":"Oleg V.","family":"Mikhailov","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Certification and Quality Management, Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Georgiy V.","family":"Girichev","sequence":"additional","affiliation":[{"name":"Department of Physics, Ivanovo State University of Chemistry and Technology, Sheremetevskiy Avenue 7, 153000 Ivanovo, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,6,24]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"67","DOI":"10.1016\/S0010-8545(00)80370-7","article-title":"Some new developments in the chemistry of metallophthalocyanines","volume":"32","author":"Kasuda","year":"1980","journal-title":"Coord. Chem. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"491","DOI":"10.1023\/A:1007054025169","article-title":"Metalloporphyrin arrays","volume":"25","author":"Sliva","year":"2000","journal-title":"Transit. Met. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1070\/RC2008v077n01ABEH003743","article-title":"Self-assembling systems based on porphyrins","volume":"77","author":"Mamardashvili","year":"2008","journal-title":"Russ. Chem. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1261","DOI":"10.1142\/S1088424619300246","article-title":"40 years with porphyrazines","volume":"23","author":"Khelevina","year":"2019","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_5","unstructured":"Thomas, A.L. (1990). Phthalocyanines. Research & Applications, CRC Press."},{"key":"ref_6","unstructured":"Lomova, T.N. (2018). Axial Coordinated Metal Porphyrins in Science and Practice, URSS."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"835","DOI":"10.1021\/cr0101454","article-title":"Subphthalocyanines: Singular nonplanar aromatic compounds-synthesis, reactivity, and physical properties","volume":"102","author":"Claessens","year":"2002","journal-title":"Chem. Rev."},{"key":"ref_8","first-page":"354","article-title":"Synthesis, characterization, and properties of subporphyrazines: A new class of nonplanar, aromatic macrocycles with absorption in the green region","volume":"11","author":"Esperanza","year":"2004","journal-title":"Chem.\u2014A Eur. J."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"3435","DOI":"10.1002\/adfm.200900524","article-title":"Perfluorinated Subphthalocyanine as a New Acceptor Material in a Small-Molecule Bilayer Organic Solar Cell","volume":"19","author":"Gommans","year":"2009","journal-title":"Adv. Funct. Mater."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1934","DOI":"10.1021\/am1002603","article-title":"Fluorinated phenoxy boron subphthalocyanines in organic light-emitting diodes","volume":"2","author":"Morse","year":"2010","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"352","DOI":"10.1002\/aenm.201100036","article-title":"Halogenated boron subphthalocyanines as light harvesting electron acceptors in organic photovoltaics","volume":"1","author":"Sullivan","year":"2011","journal-title":"Adv. Energy Mater."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"561","DOI":"10.1002\/adfm.201101782","article-title":"Boron subphthalocyanine chloride as an electron acceptor for high-voltage fullerene-free organic photovoltaics","volume":"22","author":"Beaumont","year":"2012","journal-title":"Adv. Funct. Mater."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"5055","DOI":"10.1021\/am3015197","article-title":"Boron subphthalocyanines as organic electronic materials","volume":"4","author":"Morse","year":"2012","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2192","DOI":"10.1021\/cr400088w","article-title":"Subphthalocyanines, Subporphyrazines, and Subporphyrins: Singular Nonplanar Aromatic Systems","volume":"114","author":"Claessens","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"18896","DOI":"10.1039\/C4CP02733G","article-title":"High voltage hybrid organic photovoltaics using a zinc oxide acceptor and a subphthalocyanine donor","volume":"16","author":"Dearden","year":"2014","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"14813","DOI":"10.1021\/jp503578g","article-title":"Acceptor properties of boron subphthalocyanines in fullerene free photovoltaics","volume":"118","author":"Beaumont","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"7345","DOI":"10.1039\/C5TA00715A","article-title":"Solution-processed boron subphthalocyanine derivatives as acceptors for organic bulk-heterojunction solar cells","volume":"3","author":"Ebenhoch","year":"2015","journal-title":"J. Mater. Chem. A"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3121","DOI":"10.1021\/acs.jpclett.5b01254","article-title":"Boron Subphthalocyanines as Triplet Harvesting Materials within Organic Photovoltaics","volume":"6","author":"Castrucci","year":"2015","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"69813","DOI":"10.1039\/C5RA12004G","article-title":"Subphthalocyanine as hole transporting material for perovskite solar cells","volume":"5","author":"Sfyri","year":"2015","journal-title":"RSC Adv."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"548","DOI":"10.6060\/mhc171038s","article-title":"Thiadiazole Fused Subporphyrazines as Acceptors in Organic Photovoltaic Cells","volume":"10","author":"Pakhomov","year":"2017","journal-title":"Macroheterocycles"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"31628","DOI":"10.1039\/C7CP04876A","article-title":"Interfacial electronic structure of Cl6SubPc non-fullerene acceptors in organic photovoltaics using soft X-ray spectroscopies","volume":"19","author":"Lee","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"888","DOI":"10.1016\/j.dyepig.2018.11.006","article-title":"Subphthalocyanine azaanalogues\u2014Boron(III) subporphyrazines with fused pyrazine fragments","volume":"162","author":"Stuzhin","year":"2019","journal-title":"Dye. Pigment."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"107584","DOI":"10.1016\/j.dyepig.2019.107584","article-title":"Influence of heteroatom substitution in benzene rings on structural features and spectral properties of subphthalocyanine dyes","volume":"170","author":"Hamdoush","year":"2019","journal-title":"Dye. Pigment."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2641","DOI":"10.1021\/acs.inorgchem.9b03529","article-title":"Axial\/Peripheral Chloride\/Fluoride-Substituted Boron Subphthalocyanines as Electron Acceptors","volume":"59","author":"Mizrahi","year":"2020","journal-title":"Inorg. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"108944","DOI":"10.1016\/j.dyepig.2020.108944","article-title":"Subphthalocyanine-type dye with enhanced electron affinity: Effect of combined azasubstitution and peripheral chlorination","volume":"185","author":"Skvortsov","year":"2021","journal-title":"Dye. Pigment."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2315","DOI":"10.1080\/00268976.2017.1333644","article-title":"Thirty years of density functional theory in computational chemistry: An overview and extensive assessment of 200 density functionals","volume":"115","author":"Mardirossian","year":"2017","journal-title":"Mol. Phys."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-functional exchange-energy approximation with correct asymptotic behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"16533","DOI":"10.1103\/PhysRevB.54.16533","article-title":"Generalized gradient approximation for the exchange-correlation hole of a many-electron system","volume":"54","author":"Perdew","year":"1996","journal-title":"Phys. Rev. B"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"49","DOI":"10.1126\/science.aah5975","article-title":"Density functional theory is straying from the path toward the exact functional","volume":"355","author":"Medvedev","year":"2017","journal-title":"Science"},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Mikhailov, O.V., and Chachkov, D.V. (2020). DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands. Int. J. Mol. Sci., 21.","DOI":"10.3390\/ijms21239085"},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Chachkov, D.V., and Mikhailov, O.V. (2023). Heteroligand Iron(V) Complexes Containing Porphyrazine, trans-Di[benzo]porphyrazine or Tetra[benzo]porphyrazine, Oxo and Fluoro Ligands: DFT Quantum-Chemical Study. Int. J. Mol. Sci., 24.","DOI":"10.3390\/ijms24076442"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"282","DOI":"10.3390\/quantum5010019","article-title":"Molecular Structure of M(N13) Compounds with 12-Membered Nitrogen-Containing Cycle and Axial Nitrogen Atom (M = Mn, Fe): Quantum-Chemical Design by DFT Method","volume":"5","author":"Mikhailov","year":"2023","journal-title":"Quantum Rep."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"5121","DOI":"10.1021\/jp060231d","article-title":"Comparative DFT study of van der Waals complexes: Rare-gas dimers, alkaline-earth dimers, zinc dimer, and zinc-rare-gas dimers","volume":"110","author":"Zhao","year":"2006","journal-title":"J. Phys. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"ref_35","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Gaussian 09, Revision A.01, Gaussian, Inc."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"399","DOI":"10.1080\/0144235X.2016.1192262","article-title":"What is NBO analysis and how is it useful?","volume":"35","author":"Weinhold","year":"2016","journal-title":"Int. Rev. Phys. Chem."},{"key":"ref_37","unstructured":"Ochterski, J.W. (2000). Thermochemistry in Gaussian, Gaussian, Inc."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/25\/13\/6897\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T15:03:19Z","timestamp":1760108599000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/25\/13\/6897"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,6,24]]},"references-count":37,"journal-issue":{"issue":"13","published-online":{"date-parts":[[2024,7]]}},"alternative-id":["ijms25136897"],"URL":"https:\/\/doi.org\/10.3390\/ijms25136897","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,6,24]]}}}