{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T14:12:29Z","timestamp":1788963149206,"version":"build-2803163510"},"reference-count":43,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2024,7,30]],"date-time":"2024-07-30T00:00:00Z","timestamp":1722297600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100010438","name":"Poznan University of Medical Sciences","doi-asserted-by":"publisher","award":["JAK0000056"],"award-info":[{"award-number":["JAK0000056"]}],"id":[{"id":"10.13039\/501100010438","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The presented studies aimed to evaluate the peripheral coordinating properties of a novel porphyrinoid family representative preceded by its synthesis for potential sensing purposes. Two synthetic pathways were employed to a obtain maleonitrile derivative, further used as a starting material in the cyclotetramerization reaction. In the first one, DAMN was used in sequential double-reductive alkylation with 2-thiophene-carboxyaldehyde and sodium borohydride. In the second, DAMN was used in a one-pot reaction with 2-thiophene-carboxyaldehyde in the presence of a 5-ethyl-2-methylpyridine borane complex in methanol and acetic acid. Following the Linstead approach, the cyclization reaction led to a novel symmetrical magnesium(II) octaaminoporphyrazine with methyl(2-thiophenylmethylene) substituents. The macrocycle\u2019s electrochemical properties were assessed by cyclic and differential pulse voltammetries revealing one reduction and two oxidation peak potentials. The additional spectroelectrochemical measurements showed formation of a cationic form of the macrocycle at an applied potential of 0.6 V. The coordinating properties due to the palladium ion of novel porphyrazines were measured with the use of titration combined with UV\u2013vis spectrometry. The titration of Pd2+ revealed the good sensing activity of porphyrazine in the range of 0.1 to 5 palladium molar equivalents. In addition, Pd2+ ions coordination was also assessed by electrochemical studies, indicating the peak potential shift of 0.1 V in the presence of metal cations. DFT calculations showed the good agreement between theoretical and experimental data in the UV\u2013vis and 1H NMR studies.<\/jats:p>","DOI":"10.3390\/molecules29153610","type":"journal-article","created":{"date-parts":[[2024,7,30]],"date-time":"2024-07-30T17:08:34Z","timestamp":1722359314000},"page":"3610","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Magnesium(II) Porphyrazine with Thiophenylmethylene Groups-Synthesis, Electrochemical Characterization, UV\u2013Visible Titration with Palladium Ions, and Density Functional Theory Calculations"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0798-4626","authenticated-orcid":false,"given":"Wojciech","family":"Szczolko","sequence":"first","affiliation":[{"name":"Chair and Department of Chemical Technology of Drugs, Poznan University of Medical Sciences, Rokietnicka 3, 60-806 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kyrylo","family":"Chornovolenko","sequence":"additional","affiliation":[{"name":"Chair and Department of Chemical Technology of Drugs, Poznan University of Medical Sciences, Rokietnicka 3, 60-806 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6279-4887","authenticated-orcid":false,"given":"Jacek","family":"Kujawski","sequence":"additional","affiliation":[{"name":"Chair and Department of Organic Chemistry, Poznan University of Medical Sciences, Rokietnicka 3, 60-806 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6141-3322","authenticated-orcid":false,"given":"Zbigniew","family":"Dutkiewicz","sequence":"additional","affiliation":[{"name":"Chair and Department of Chemical Technology of Drugs, Poznan University of Medical Sciences, Rokietnicka 3, 60-806 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8446-4758","authenticated-orcid":false,"given":"Tomasz","family":"Koczorowski","sequence":"additional","affiliation":[{"name":"Chair and Department of Chemical Technology of Drugs, Poznan University of Medical Sciences, Rokietnicka 3, 60-806 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2024,7,30]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"473","DOI":"10.1002\/0471227110.ch8","article-title":"Peripherally Functionalized Porphyrazines: Novel Metallomacrocycles with Broad, Untapped Potential","volume":"50","author":"Michel","year":"2001","journal-title":"Prog. Inorg. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1129","DOI":"10.1142\/S1088424604000490","article-title":"The Chemistry of Porphyrazines: An Overview","volume":"8","author":"Stuzhin","year":"2004","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"555","DOI":"10.1002\/1099-1409(200008)4:5<555::AID-JPP271>3.0.CO;2-6","article-title":"Modification of \u03b2-Positions in Porphyrazines by Substitution Reactions","volume":"4","author":"Khelevina","year":"2000","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"235","DOI":"10.1071\/CH07445","article-title":"Porphyrazines: Designer Macrocycles by Peripheral Substituent Change","volume":"61","author":"Fuchter","year":"2008","journal-title":"Aust. J. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"179","DOI":"10.1016\/S0898-8838(08)60118-X","article-title":"Magnetism of Heterobimetallics: Toward Molecular-Based Magnets","volume":"Volume 43","author":"Kahn","year":"1995","journal-title":"Advances in Inorganic Chemistry"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1039\/cs9942300327","article-title":"1,10-Phenanthroline: A Versatile Ligand","volume":"23","author":"Sammes","year":"1994","journal-title":"Chem. Soc. Rev."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1016\/S0020-1693(01)00325-5","article-title":"Phenanthroline-Appended Porphyrazines: Synthesis and Conversion into Solitaire Ru(II) Complexes","volume":"317","author":"Montalban","year":"2001","journal-title":"Inorganica Chim. Acta"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"372","DOI":"10.1016\/j.dyepig.2012.09.002","article-title":"Synthesis and Characterization of Porphyrazines as Novel Extractants for the Removal of Ag(I) and Hg(II) from Aqueous Solution","volume":"96","author":"Kabay","year":"2013","journal-title":"Dye. Pigment."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"739","DOI":"10.1016\/j.inoche.2009.05.036","article-title":"Synthesis and Electron Donating Property of Novel Porphyrazines Containing Tetrathiacrown Ether-Linked Tetrathiafulvalene Moieties","volume":"12","author":"Hou","year":"2009","journal-title":"Inorg. Chem. Commun."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2579","DOI":"10.1016\/j.poly.2009.05.033","article-title":"Synthesis, characterization and spectroscopic properties of novel periphery \u2013functionalized unsymmetrical porphyrazines containing mixed dithienylpyrrolyl and dimethylamino groups","volume":"28","author":"Goslinski","year":"2009","journal-title":"Polyhedron"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"2755","DOI":"10.1016\/j.ccr.2010.05.001","article-title":"Metallophthalocyanine-Based Molecular Materials as Catalysts for Electrochemical Reactions","volume":"254","author":"Zagal","year":"2010","journal-title":"Coord. Chem. Rev."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1016\/j.bioelechem.2006.03.025","article-title":"Electrocatalytic Activity of Cobalt Phthalocyanine CoPc Adsorbed on a Graphite Electrode for the Oxidation of Reduced L-Glutathione (GSH) and the Reduction of Its Disulfide (GSSG) at Physiological pH","volume":"70","author":"Zagal","year":"2007","journal-title":"Bioelectrochemistry"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"586","DOI":"10.1246\/cl.2007.586","article-title":"Oxidative Degradation of Organic Pollutants by Hydrogen Peroxide in the Presence of FePz(dtnCl2)4 under Visible Irradiation","volume":"36","author":"Sun","year":"2007","journal-title":"Chem. Lett."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"34","DOI":"10.1246\/cl.2004.34","article-title":"A Novel Catalyst Iron(II) Tetra(1,4-Dithin)Porphyrazine for Oxygenating Degradation of Organic Pollutants in Aqueous Solutions","volume":"33","author":"Deng","year":"2004","journal-title":"Chem. Lett."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Garrido Montalban, A., Baum, S.M., Barrett, A.G.M., and Hoffman, B.M. (2003). Studies on Seco-Porphyrazines: A Case Study on Serendipity. Dalton Trans., 2093\u20132102.","DOI":"10.1039\/b209800h"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1825","DOI":"10.1016\/S0040-4020(01)97932-3","article-title":"Singlet Oxygen in Organic Synthesis","volume":"37","author":"Wasserman","year":"1981","journal-title":"Tetrahedron"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1474","DOI":"10.1039\/C4RA09781E","article-title":"Cobalt Phthalocyanine Tetracarboxylic Acid Modified Reduced Graphene Oxide: A Sensitive Matrix for the Electrocatalytic Detection of Peroxynitrite and Hydrogen Peroxide","volume":"5","author":"Hosu","year":"2015","journal-title":"RSC Adv."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"24063","DOI":"10.1021\/acsami.5b07068","article-title":"Superior Catalytic Activity of Electrochemically Reduced Graphene Oxide Supported Iron Phthalocyanines toward Oxygen Reduction Reaction","volume":"7","author":"Liu","year":"2015","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Koczorowski, T., Cerbin-Koczorowska, M., and R\u0119bi\u015b, T. (2021). Azaporphyrins Embedded on Carbon-Based Nanomaterials for Potential Use in Electrochemical Sensing\u2014A Review. Nanomaterials, 11.","DOI":"10.3390\/nano11112861"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"108370","DOI":"10.1016\/j.dyepig.2020.108370","article-title":"Electrochemical and Catalytic Assessment of Peripheral Bromoaryl-Substituted Manganese and Iron Porphyrazines","volume":"178","author":"Koczorowski","year":"2020","journal-title":"Dye. Pigment."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"6115","DOI":"10.1016\/j.tet.2005.03.090","article-title":"Synthesis of Porphyrazine-Octaamine, Hexamine and Diamine Derivatives","volume":"61","author":"Fuchter","year":"2005","journal-title":"Tetrahedron"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"223","DOI":"10.1142\/S108842461550100X","article-title":"Effect of Polyfluorination on Self-Assembling and Electronic Properties of Thioalkyl-Porphyrazines","volume":"20","author":"Belviso","year":"2016","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_23","doi-asserted-by":"crossref","unstructured":"Hassani, M., Leda, A., Porolnik, W., Falkowski, M., R\u0119bi\u015b, T., Piskorz, J., Popenda, L., Wicinski, M., Mlynarczyk, D.T., and D\u00fczg\u00fcne\u015f, N. (2023). Synthesis, Electrochemical and Photochemical Properties of Sulfanyl Porphyrazine with Ferrocenyl Substituents. Molecules, 28.","DOI":"10.3390\/molecules28135215"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1016\/j.ccr.2007.11.025","article-title":"Ferrocene-Appended Porphyrins: Syntheses and Properties","volume":"253","author":"Bucher","year":"2009","journal-title":"Coord. Chem. Rev."},{"key":"ref_25","first-page":"751","article-title":"A New Phthalocyanine\u2013Ferrocene Conjugated Dyad","volume":"637\u2013639","author":"Torres","year":"2001","journal-title":"J. Organomet. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"223","DOI":"10.1142\/S1088424609000309","article-title":"Synthesis and Characterization of Periphery-Functionalized Porphyrazines Containing Mixed Pyrrolyl and Pyridylmethylamino Groups","volume":"13","author":"Goslinski","year":"2009","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"5152","DOI":"10.1016\/j.tetlet.2008.06.095","article-title":"Reductive Amination with 5-Ethyl-2-Methylpyridine Borane","volume":"49","author":"Burkhardt","year":"2008","journal-title":"Tetrahedron Lett."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2341","DOI":"10.1021\/jo00930a004","article-title":"Hydrogen Cyanide Chemistry. VIII. New Chemistry of Diaminomaleonitrile. Heterocyclic Synthesis","volume":"39","author":"Begland","year":"1974","journal-title":"J. Org. Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"265","DOI":"10.1016\/j.jfluchem.2011.12.003","article-title":"Synthesis, Physical\u2013Chemical Properties and in Vitro Photodynamic Activity against Oral Cancer Cells of Novel Porphyrazines Possessing Fluoroalkylthio and Dietherthio Substituents","volume":"135","author":"Piskorz","year":"2012","journal-title":"J. Fluor. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"599","DOI":"10.1007\/s00706-011-0503-9","article-title":"Experimental and Computational Study on the Reactivity of 2,3-Bis[(3-Pyridylmethyl)Amino]-2(Z)-Butene-1,4-Dinitrile, a Key Intermediate for the Synthesis of Tribenzoporphyrazine Bearing Peripheral Methyl(3-Pyridylmethyl)Amino Substituents","volume":"142","author":"Goslinski","year":"2011","journal-title":"Monatsh. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"610","DOI":"10.1016\/j.dyepig.2011.05.023","article-title":"Synthesis, Characterization, Electrochemistry and Spectroelectrochemistry of Novel Soluble Porphyrazines Bearing Unsaturated Functional Groups","volume":"92","author":"Tuncer","year":"2012","journal-title":"Dye. Pigment."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Koczorowski, T., Szczolko, W., Teubert, A., and Goslinski, T. (2021). Sulfanyl Porphyrazines with Morpholinylethyl Periphery\u2014Synthesis, Electrochemistry, and Photocatalytic Studies after Deposition on Titanium(IV) Oxide P25 Nanoparticles. Molecules, 26.","DOI":"10.3390\/molecules26082280"},{"key":"ref_33","unstructured":"BIOVIA (2012). Dassault Syst\u00e8mes, Discovery Studio, Release 3.5, Dassault Syst\u00e8mes."},{"key":"ref_34","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., and Cheeseman, J.R. (2016). Gaussian 16, Revision A.03 Gaussian, Gaussian Inc."},{"key":"ref_35","unstructured":"Parr, R.G., and Weitao, Y. (2015). Density-Functional Theory of Atoms and Molecules, Oxford University Press."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-Functional Thermochemistry. III. The Role of Exact Exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2193","DOI":"10.1063\/1.455064","article-title":"A Complete Basis Set Model Chemistry. I. The Total Energies of Closed-Shell Atoms and Hydrides of the First-Row Elements","volume":"89","author":"Petersson","year":"1988","journal-title":"J. Chem. Phys."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"5631","DOI":"10.1021\/jp000156l","article-title":"Fast Evaluation of Geometries and Properties of Excited Molecules in Solution: A Tamm-Dancoff Model with Application to 4-Dimethylaminobenzonitrile","volume":"104","author":"Cammi","year":"2000","journal-title":"J. Phys. Chem. A"},{"key":"ref_39","unstructured":"Dover (2003). Statistical Mechanics, Dover Publications."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3530","DOI":"10.1063\/1.1286806","article-title":"Nuclear Magnetic Resonance Spin\u2013Spin Coupling Constants from Coupled Perturbed Density Functional Theory","volume":"113","author":"Cremer","year":"2000","journal-title":"J. Chem. Phys."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"6823","DOI":"10.1021\/ja0551180","article-title":"Indirect NMR Spin\u2212Spin Coupling Constants 3 J (P,C) and 2 J (P,H) across the P\u2212O\u00b7\u00b7\u00b7H\u2212C Link Can Be Used for Structure Determination of Nucleic Acids","volume":"128","author":"Schneider","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"3304","DOI":"10.1021\/ct200461y","article-title":"Time-Dependent Density Functional Tight Binding: New Formulation and Benchmark of Excited States","volume":"7","author":"Trani","year":"2011","journal-title":"J. Chem. Theory Comput."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"8251","DOI":"10.1021\/ja00179a005","article-title":"Efficient Implementation of the Gauge-Independent Atomic Orbital Method for NMR Chemical Shift Calculations","volume":"112","author":"Wolinski","year":"1990","journal-title":"J. Am. Chem. Soc."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/15\/3610\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T15:26:52Z","timestamp":1760110012000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/15\/3610"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,7,30]]},"references-count":43,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2024,8]]}},"alternative-id":["molecules29153610"],"URL":"https:\/\/doi.org\/10.3390\/molecules29153610","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,7,30]]}}}