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Here, we generate such PAHs by reversible oxidation of PAH\u2010extended tetrathiafulvalenes (TTFs). Extended TTFs were thus prepared and studied for their geometrical properties (crystallography), redox properties, and UV\/Vis\/NIR\/EPR characteristics as a function of charge state. The EPR measurements of radical cations showed unique features for each PAH\u2010TTF. The dications, formally composed of fluoreno[3,2\u2010<jats:italic>b<\/jats:italic>]fluorene and diindeno[1,2\u2010<jats:italic>b<\/jats:italic>:1\u2032,2\u2032\u2010<jats:italic>i<\/jats:italic>]anthracene cores, were experimentally found to exhibit singlet ground states. For the latter, calculations reveal the closed shell, quinoid singlet state to be isoenergetic with the open shell singlet diradical. Each charge state exhibited unique optical properties with radical cations absorbing strongly in the NIR region with signatures from \u03c0\u2010dimers for the large core. The experimental results were paralleled and supported by detailed computations, including spin density distribution calculations, EPR simulations, and nucleus independent chemical shift (NICS) <jats:italic>xy<\/jats:italic> scans.<\/jats:p>","DOI":"10.1002\/chem.202302688","type":"journal-article","created":{"date-parts":[[2023,11,6]],"date-time":"2023-11-06T10:19:12Z","timestamp":1699265952000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Extended Tetrathiafulvalenes with Fluoreno[3,2\u2010<i>b<\/i>]fluorene and Diindeno[1,2\u2010<i>b<\/i>\u2009:\u20091\u2032,2\u2032\u2010<i>i<\/i>]anthracene Cores"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8982-4756","authenticated-orcid":false,"given":"Jeppe","family":"Granh\u00f8j","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Copenhagen  Universitetsparken 5 DK-2100 Copenhagen \u00d8 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