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X\u2010ray structures of the parent TPTBP complexes, the dications, and singly oxidized species [(TPTBP)Cu<jats:sup>II<\/jats:sup>]<jats:sup><jats:bold>\u22c5<\/jats:bold>+<\/jats:sup>[SbF<jats:sub>6<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (<jats:bold>11<\/jats:bold>) reveal that the use of TPTBP rather than a porphyrin ligand reduces the degree of nonplanarity in the 16\u03c0\u2010electron species relative to the parent 18\u03c0 complex. Significant high\u2010field shifts of the <jats:sup>1<\/jats:sup>H\u2005NMR signals of the outer ring protons and large positive values in calculations of nucleus\u2010independent chemical shifts on the central cavity of the porphyrin ring provide unambiguous evidence for the antiaromatic character of the 16\u03c0 Zn<jats:sup>II<\/jats:sup> species. A combination of magnetic circular dichroism spectroscopic studies and TD\u2010DFT calculations on both the Zn<jats:sup>II<\/jats:sup> and Cu<jats:sup>II<\/jats:sup> species demonstrates that the main electronic bands of the dicationic species can be readily assigned by using Michl\u2019s 4<jats:italic>N<\/jats:italic> perimeter model. Femtosecond transient absorption studies clearly demonstrated that the number of \u03c0 electrons on the inner ligand perimeter and the configuration of the central metal ion play a critical role in the excited\u2010state relaxation dynamics. Redox potentials for conversion between the 16\u03c0, 17\u03c0, and 18\u03c0 systems were measured by cyclic voltammetry in dichloromethane and benzonitrile, and UV\/Vis spectra of each oxidation\/reduction product were monitored by thin\u2010layer spectroelectrochemistry.<\/jats:p>","DOI":"10.1002\/chem.201101846","type":"journal-article","created":{"date-parts":[[2012,2,14]],"date-time":"2012-02-14T15:34:08Z","timestamp":1329233648000},"page":"3566-3581","source":"Crossref","is-referenced-by-count":27,"title":["Synthesis, Characterization, and Spectroscopic Analysis of Antiaromatic Benzofused 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