{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,7]],"date-time":"2026-03-07T11:04:58Z","timestamp":1772881498817,"version":"3.50.1"},"reference-count":53,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2025,4,18]],"date-time":"2025-04-18T00:00:00Z","timestamp":1744934400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-2247214"],"award-info":[{"award-number":["CHE-2247214"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE 1337497"],"award-info":[{"award-number":["CHE 1337497"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-0722385"],"award-info":[{"award-number":["CHE-0722385"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"name":"National Science Foundation MRI Program","award":["CHE-2247214"],"award-info":[{"award-number":["CHE-2247214"]}]},{"name":"National Science Foundation MRI Program","award":["CHE 1337497"],"award-info":[{"award-number":["CHE 1337497"]}]},{"name":"National Science Foundation MRI Program","award":["CHE-0722385"],"award-info":[{"award-number":["CHE-0722385"]}]},{"name":"NSF MRI program","award":["CHE-2247214"],"award-info":[{"award-number":["CHE-2247214"]}]},{"name":"NSF MRI program","award":["CHE 1337497"],"award-info":[{"award-number":["CHE 1337497"]}]},{"name":"NSF MRI program","award":["CHE-0722385"],"award-info":[{"award-number":["CHE-0722385"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A series of porphyrinoids fused to highly electron-withdrawing bis(thiadiazolo)benzene units have been prepared and spectroscopically characterized. These structures have modified chromophores and exhibit large bathochromic shifts. The nickel(II), copper(II) and zinc complexes of a bis(thiadiazolo)benzoporphyrin were prepared, and these showed strong absorptions above 600 nm that shifted to longer wavelengths with increasing atomic number for the coordinated metal cations. Although the investigated porphyrinoids were poorly soluble, proton NMR data could be obtained, and these demonstrated that the structures possess global aromatic character. This was confirmed with nucleus-independent chemical shift (NICS) calculations and anisotropy of induced current density (AICD) plots. The AICD plots also demonstrate that the fused heterocyclic unit is disconnected from the porphyrinoid \u03c0-system, and in this respect, it differs from phenanthroline-fused porphyrinoids as it shows the presence of extended conjugation pathways.<\/jats:p>","DOI":"10.3390\/molecules30081822","type":"journal-article","created":{"date-parts":[[2025,4,18]],"date-time":"2025-04-18T06:23:56Z","timestamp":1744957436000},"page":"1822","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Synthesis and Spectroscopic Characterization of Bis(thiadiazolo)benzoporphyrinoids: Insights into the Properties of Porphyrin-Type Systems with Strongly Electron-Withdrawing \u03b2,\u03b2\u2019-Fused Rings"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0050-0385","authenticated-orcid":false,"given":"Timothy D.","family":"Lash","sequence":"first","affiliation":[{"name":"Department of Chemistry, Illinois State University, Normal, IL 61790, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Catherine M.","family":"Cillo","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Illinois State University, Normal, IL 61790, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0813-0486","authenticated-orcid":false,"given":"Deyaa I.","family":"AbuSalim","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Illinois State University, Normal, IL 61790, USA"},{"name":"Department of Chemistry, Rowan University, Glassboro, NJ 08028, USA"},{"name":"STEM Department, Rowan College of South Jersey, Vineland, NJ 08360, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,4,18]]},"reference":[{"key":"ref_1","first-page":"125","article-title":"Synthesis of Novel Porphyrinoid Chromophores","volume":"Volume 2","author":"Kadish","year":"2000","journal-title":"The Porphyrin Handbook"},{"key":"ref_2","first-page":"1","article-title":"Synthesis of Porphyrins with Fused Aromatic Rings","volume":"Volume 2","author":"Smith","year":"2010","journal-title":"Handbook of Porphyrin Science\u2014With Applications to Chemistry, Physics, Material Science, Engineering, Biology and Medicine"},{"key":"ref_3","first-page":"1","article-title":"The Synthesis of \u03c0-Extended Porphyrins","volume":"Volume 13","author":"Smith","year":"2011","journal-title":"Handbook of Porphyrin Science\u2014With Applications to Chemistry, Physics, Material Science, Engineering, Biology and Medicine"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1337","DOI":"10.1071\/CH9771337","article-title":"The Chemistry of Pyrrolic Compounds. XXXVII. Monobenzoporphyrins: The Rhodoporphyrin of Petroleum Deposits","volume":"30","author":"Clezy","year":"1977","journal-title":"Aust. J. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"166","DOI":"10.1021\/ef00038a001","article-title":"Geochemical Origins of Sedimentary Benzoporphyrins and Tetrahydrobenzoporphyrins","volume":"7","author":"Lash","year":"1993","journal-title":"Energy Fuels"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/0040-4020(94)00963-U","article-title":"Porphyrins with Exocyclic Rings. Part 5. Synthesis of a Naphtho[1,2-b]porphyrin","volume":"51","author":"Lash","year":"1995","journal-title":"Tetrahedron"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"874","DOI":"10.1021\/jo040269r","article-title":"Synthesis of Isomeric Angularly Annealed Dinaphthoporphyrin Systems:\u2009 Examination of the Relative Positioning and Orientation of Ring Fusion as Factors Influencing the Porphyrin Chromophore","volume":"70","author":"Manley","year":"2005","journal-title":"J. Org. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"3998","DOI":"10.1021\/jo980043m","article-title":"Porphyrins with Exocyclic Rings. 11. Synthesis and Characterization of Phenanthroporphyrins, a New Class of Modified Porphyrin Chromophores","volume":"63","author":"Novak","year":"1998","journal-title":"J. Org. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"132481","DOI":"10.1016\/j.tet.2021.132481","article-title":"Extended Porphyrinoid Chromophores: Heteroporphyrins Fused to Phenanthrene and Acenaphthylene","volume":"100","author":"Lash","year":"2021","journal-title":"Tetrahedron"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1787","DOI":"10.1016\/j.tet.2010.01.046","article-title":"Porphyrins with Exocyclic Rings. Part 24. Synthesis and Spectroscopic Properties of Pyrenoporphyrins, Potential Building Blocks for Porphyrin Molecular Wires","volume":"66","author":"Gandhi","year":"2010","journal-title":"Tetrahedron"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"16276","DOI":"10.1021\/acs.joc.2c01859","article-title":"Synthesis of Chrysoporphyrins and a Related Benzopyrene-Fused System","volume":"87","author":"Lash","year":"2022","journal-title":"J. Org. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"8455","DOI":"10.1021\/jo9815655","article-title":"Porphyrins with Exocyclic Rings. 13. Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings","volume":"63","author":"Lash","year":"1998","journal-title":"J. Org. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1530","DOI":"10.1021\/jo991730w","article-title":"Porphyrins with Exocyclic Rings. Part 14. Synthesis of Tetraacenaphthoporphyrins, a New Family of Highly Conjugated Porphyrins with Record Breaking Long Wavelength Electronic Absorptions","volume":"65","author":"Spence","year":"2000","journal-title":"J. Org. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"11615","DOI":"10.1016\/j.tet.2005.09.090","article-title":"Porphyrins with Exocyclic Rings. Part 20: Synthesis and Spectroscopic Characterization of Porphyrins with Fused 2,1,3-Benzoxadiazole and 2,1,3-Benzoselenadiazole Moieties","volume":"61","author":"Cillo","year":"2005","journal-title":"Tetrahedron"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1002\/jpp.313","article-title":"Modification of the Porphyrin Chromophore by Ring Fusion: Identifying Trends due to Annelation of the Porphyrin Nucleus","volume":"5","author":"Lash","year":"2001","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"16493","DOI":"10.1021\/acs.joc.4c01760","article-title":"Assessment of Conjugation Pathways in N-Methylporphyrins that Are Fused to Acenaphthylene, Phenanthrene, or Pyrene: Evidence for the Presence of Alternative Aromatic Circuits","volume":"89","author":"Salrin","year":"2024","journal-title":"J. Org. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"e202302013","DOI":"10.1002\/chem.202302013","article-title":"Naphthodithiophene-Fused Porphyrins: Synthesis, Characterization, and Impact of Extended Conjugation on Aromaticity","volume":"29","author":"Cooper","year":"2023","journal-title":"Chem. Eur. J."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"8020","DOI":"10.1021\/jo001216m","article-title":"Porphyrins with Exocyclic Rings. 15. Synthesis of Quino- and Isoquinoporphyrins, Aza Analogues of the Naphthoporphyrins","volume":"65","author":"Lash","year":"2000","journal-title":"J. Org. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"9441","DOI":"10.1016\/0040-4039(95)02100-0","article-title":"Porphyrin Synthesis by the \u201c3 + 1\u201d Methodology: A Superior Approach for the Preparation of Porphyrins with Fused 9,10-Phenanthroline Subunits","volume":"36","author":"Lin","year":"1995","journal-title":"Tetrahedron Lett."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"11601","DOI":"10.1016\/j.tet.2005.09.089","article-title":"Porphyrins with Exocyclic Rings. Part 19: Efficient Syntheses of Phenanthrolinoporphyrins","volume":"61","author":"Lash","year":"2005","journal-title":"Tetrahedron"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"952","DOI":"10.1021\/acs.joc.1c02063","article-title":"Synthesis of a Series of Tropone-fused Porphyrinoids","volume":"87","author":"Cramer","year":"2022","journal-title":"J. Org. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"8","DOI":"10.1021\/acs.joc.4c01511","article-title":"Synthesis, Protonation and Aromatic Characteristics of a Series of 1,10-Phenanthroline-Fused Porphyrinoids","volume":"90","author":"Ujah","year":"2025","journal-title":"J. Org. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"3583","DOI":"10.1016\/S0040-4039(00)00468-8","article-title":"Coplanar Conjugated \u03b2- Nitroporphyrins and Some Aspects of Nitration of Porphyrins with N2O4","volume":"41","author":"Siri","year":"2000","journal-title":"Tetrahedron Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"6266","DOI":"10.1021\/jacs.3c14390","article-title":"Effects of Electron-Withdrawing and Electron-Donating Groups on Aromaticity in Cyclic Conjugated Polyenes","volume":"146","author":"Ko","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"4860","DOI":"10.1021\/jo020267b","article-title":"Conjugated Macrocycles Related to the Porphyrins. Part 21. Synthesis, Spectroscopy, Electrochemistry and Structural Characterization of Carbaporphyrins","volume":"67","author":"Lash","year":"2002","journal-title":"J. Org. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"9076","DOI":"10.1021\/jo981872a","article-title":"Conjugated Macrocycles Related to the Porphyrins. Part 12. Oxybenzi- and Oxypyriporphyrins: Aromaticity and Conjugation in Highly Modified Porphyrinoid Structures","volume":"63","author":"Lash","year":"1998","journal-title":"J. Org. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"152576","DOI":"10.1016\/j.tetlet.2020.152576","article-title":"Exploring the Limitations of the MacDonald \u20183 + 1\u2019 Condensation in the Preparation of Porphyrins with Fused Electron-withdrawing Heterocyclic Rings: Synthesis of a Bis(thiadiazolo)benzoporphyrin and a Related Benzocarbaporphyrin","volume":"61","author":"Cillo","year":"2020","journal-title":"Tetrahedron Lett."},{"key":"ref_28","unstructured":"Examples of thiadiazoloporphyrazines have been reported:\n        DonzelloM.P.ErcolaniC.KadishK.M.RicciardiG.RosaA.StuzhinP.A.Tetrakis(thiadiazolo)porphyrinazines. 5. Electrochemical and DFT\/TDDFT Studies of the Free-Base Macrocycle and Its MgII, ZnII, and CuII ComplexesInorg. Chem.2007464145415710.1021\/ic070038d"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1055\/s-1998-2041","article-title":"New One-Step Synthesis of 3,4-Disubstituted Pyrrole-2,5-dicarbaldehydes","volume":"1998","author":"Tardieux","year":"1998","journal-title":"Synthesis"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"13050","DOI":"10.1021\/acs.joc.0c01737","article-title":"Synthesis and Characterization of N-Methylporphyrins, Heteroporphyrins, Carbaporphyrins, and Related Systems","volume":"85","author":"Latham","year":"2020","journal-title":"J. Org. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2783","DOI":"10.1135\/cccc19652783","article-title":"Synthetic Reactions of Dimethylformamide. XXII. Formation and Preparation of Formyl Derivatives of Indene","volume":"30","author":"Arnold","year":"1965","journal-title":"Collect. Czech. Chem. Commun."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"944","DOI":"10.1002\/chem.19960020808","article-title":"Conjugated Macrocycles Related to the Porphyrins. Part 6. Oxypyriporphyrin, the First Fully Aromatic Porphyrinoid Macrocycle with a Pyridine Subunit","volume":"2","author":"Lash","year":"1996","journal-title":"Chem. Eur. J."},{"key":"ref_33","first-page":"1","article-title":"NMR Spectroscopy of Diamagnetic Porphyrins","volume":"Volume 5","author":"Kadish","year":"2000","journal-title":"The Porphyrin Handbook"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1039\/cs9952400019","article-title":"Photosensitizers of the Porphyrin and Phthalocyanine Series for Photodynamic Therapy","volume":"24","author":"Bonnett","year":"1995","journal-title":"Chem. Soc. Rev."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"340","DOI":"10.1039\/B915149B","article-title":"The Role of Porphyrin Chemistry in Tumor Imaging and Photodynamic Therapy","volume":"40","author":"Ethirajan","year":"2011","journal-title":"Chem. Soc. Rev."},{"key":"ref_36","unstructured":"Smith, K.M. (1975). Porphyrins and Metalloporphyrins, Elsevier."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2441","DOI":"10.1016\/0040-4020(82)87025-7","article-title":"The NMR Spectra of Porphyrins-19. 13C and Proton NMR Spectra of Metal-free porphyrins with the Type-IX Substituent Orientation, and of their Zinc(II) Complexes","volume":"38","author":"Smith","year":"1982","journal-title":"Tetrahedron"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2313","DOI":"10.1021\/acs.chemrev.6b00326","article-title":"Carbaporphyrinoid Systems","volume":"117","author":"Lash","year":"2017","journal-title":"Chem. Rev."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"315","DOI":"10.1021\/ja309434t","article-title":"Description of Aromaticity in Porphyrinoids","volume":"135","author":"Wu","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1021\/ar950033x","article-title":"First-Principles Quantum Chemical Studies of Porphyrins","volume":"31","author":"Ghosh","year":"1998","journal-title":"Acc. Chem. Res."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"11718","DOI":"10.1021\/jp310480d","article-title":"Validity and Limitations of the Bridged Annulene Model for Porphyrins","volume":"116","author":"Aihara","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"14215","DOI":"10.1039\/C5CP01306B","article-title":"Predicting the Degree of Aromaticity of Novel Carbaporphyrinoids","volume":"17","author":"Valiev","year":"2015","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"AbuSalim, D.I., and Lash, T.D. (2023). Aromatic Character and Relative Stability of Pyrazoloporphyrin Tautomers and Related Protonated Species: Insights into How Pyrazole Changes the Properties of Carbaporphyrinoid Systems. Molecules, 28.","DOI":"10.3390\/molecules28062854"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"6317","DOI":"10.1021\/ja960582d","article-title":"Nucleus-Independent Chemical Shifts: A Simple and Efficient Aromaticity Probe","volume":"118","author":"Schleyer","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"3758","DOI":"10.1021\/cr0300901","article-title":"Anisotropy of Induced Current Density (ACID), a General Method to Quantify and Visualize Electronic Delocalization","volume":"105","author":"Geuenich","year":"2005","journal-title":"Chem. Rev."},{"key":"ref_46","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2019). Gaussian 16. Revision C.01, Gaussian, Inc."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"294","DOI":"10.1002\/jcc.540040303","article-title":"Efficient Diffuse Function-augmented Basis Sets for Anion Calculations. III. The 3-21+G Basis Set for First-Row Elements, Li-F","volume":"4","author":"Clark","year":"1983","journal-title":"J. Comput. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"724","DOI":"10.1063\/1.1674902","article-title":"Self-Consistent Molecular-Orbital Methods. IX. An Extended Gaussian-Type Basis for Molecular-Orbital Studies of Organic Molecules","volume":"54","author":"Ditchfield","year":"1971","journal-title":"J. Chem. Phys."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1007\/BF00533485","article-title":"The Influence of Polarization Functions on Molecular Orbital Hydrogenation Energies","volume":"28","author":"Hariharan","year":"1973","journal-title":"Theor. Chim. Acta"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"2257","DOI":"10.1063\/1.1677527","article-title":"Self-Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian-Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules","volume":"56","author":"Hehre","year":"1972","journal-title":"J. Chem. Phys."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"1007","DOI":"10.1063\/1.456153","article-title":"Gaussian Basis Sets for use in Correlated Molecular Calculations. I. The Atoms Boron through Neon and Hydrogen","volume":"90","author":"Dunning","year":"1989","journal-title":"J. Chem. Phys."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"3842","DOI":"10.1021\/cr030088+","article-title":"Nucleus-Independent Chemical Shifts (NICS) as an Aromaticity Criterion","volume":"105","author":"Chen","year":"2005","journal-title":"Chem. Rev."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"3214","DOI":"10.1021\/jp0034426","article-title":"Delocalization of Electrons in Molecules","volume":"105","author":"Herges","year":"2001","journal-title":"J. Phys. Chem. A"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/8\/1822\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T17:17:11Z","timestamp":1760030231000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/8\/1822"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,4,18]]},"references-count":53,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2025,4]]}},"alternative-id":["molecules30081822"],"URL":"https:\/\/doi.org\/10.3390\/molecules30081822","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,4,18]]}}}