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Herein we present the synthesis of such compounds with the azulenoazulene further expanded by annulation to benzene, naphthalene, or thiophene rings. Moreover, unsymmetrical donor\u2010acceptor chromophores with one DTF and one carbonyl at the central core are presented. The effect of the odd\u2010membered rings of the polycyclic aromatic hydrocarbon cores on the geometrical features and the extent of bond conjugation in these systems were investigated by UV\/Vis absorption spectroscopy, (spectro)electrochemical studies, X\u2010ray and electron diffraction, and computational studies. Altogether these studies reveal that, upon oxidation, the non\u2010planar core of the bis(benzo)\u2010fused dihydro\u2010azulenoazulene\u2010extended TTF generates a large 22\u03c0\u2010aromatic system (together with two 6\u03c0\u2010aromatic 1,3\u2010dithiolium appendages) characterized by significant bond length equalizations. The dication formed by oxidation is EPR silent, indicating a singlet ground state. Computations reveal that the closed\u2010shell singlet species and its open\u2010shell singlet counterpart are nearly degenerate and of lower energy than a triplet species. According to cyclic voltammetry, the compounds can be oxidized further and present multi\u2010redox systems.<\/jats:p>","DOI":"10.1002\/anie.202422275","type":"journal-article","created":{"date-parts":[[2024,12,23]],"date-time":"2024-12-23T17:35:06Z","timestamp":1734975306000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Extended Tetrathiafulvalene Multi\u2010Redox Systems Incorporating 4,5\u2010Dihydroazuleno[2,1,8\u2010<i>ija<\/i>]azulene Cores"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0661-6351","authenticated-orcid":false,"given":"Viktor","family":"Bliksted Roug Pedersen","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Copenhagen  Universitetsparken 5 DK-2100 Copenhagen \u00d8 Denmark"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6527-1982","authenticated-orcid":false,"given":"Michal","family":"Zalibera","sequence":"additional","affiliation":[{"name":"Institute of Physical Chemistry and Chemical Physics Slovak University of Technology in Bratislava  Radlinsk\u00e9ho 9 SK-81237 Bratislava Slovak Republic"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fr\u00e9d\u00e9ric","family":"Lirette","sequence":"additional","affiliation":[{"name":"D\u00e9partement de chimie and Centre de Recherche sur les Mat\u00e9riaux Avanc\u00e9s (CERMA) Universit\u00e9 Laval  1045 Ave de la M\u00e9decine Qu\u00e9bec QC Canada G1V0A6 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-1175-2636","authenticated-orcid":false,"given":"J\u00e9r\u00e9mie","family":"Ouellette","sequence":"additional","affiliation":[{"name":"D\u00e9partement de chimie and Centre de Recherche sur les Mat\u00e9riaux Avanc\u00e9s (CERMA) Universit\u00e9 Laval  1045 Ave de la M\u00e9decine Qu\u00e9bec QC Canada G1V0A6 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7820-907X","authenticated-orcid":false,"given":"Arianna","family":"Lanza","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Copenhagen  Universitetsparken 5 DK-2100 Copenhagen \u00d8 Denmark"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Israel","family":"Fern\u00e1ndez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Org\u00e1nica and Centro de Innovaci\u00f3n en Qu\u00edmica Avanzada (ORFEO-CINQA) Facultad de Ciencias Qu\u00edmicas Universidad Complutense de Madrid  28040 Madrid Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6071-3932","authenticated-orcid":false,"given":"Peter","family":"Rapta","sequence":"additional","affiliation":[{"name":"Institute of Physical Chemistry and Chemical Physics Slovak University of Technology in Bratislava  Radlinsk\u00e9ho 9 SK-81237 Bratislava Slovak Republic"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9259-9051","authenticated-orcid":false,"given":"Jean\u2010Fran\u00e7ois","family":"Morin","sequence":"additional","affiliation":[{"name":"D\u00e9partement de chimie and Centre de Recherche sur les Mat\u00e9riaux Avanc\u00e9s (CERMA) Universit\u00e9 Laval  1045 Ave de la M\u00e9decine Qu\u00e9bec QC Canada G1V0A6 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8377-0788","authenticated-orcid":false,"given":"Mogens","family":"Br\u00f8ndsted Nielsen","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Copenhagen  Universitetsparken 5 DK-2100 Copenhagen \u00d8 Denmark"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,1,9]]},"reference":[{"key":"e_1_2_10_1_1","unstructured":"\u00a0"},{"key":"e_1_2_10_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196401651"},{"key":"e_1_2_10_3_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac198254050939"},{"key":"e_1_2_10_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201402077"},{"key":"e_1_2_10_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00185D"},{"key":"e_1_2_10_6_2","doi-asserted-by":"crossref","unstructured":"Y. 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