Scrutinizing the chemical nature and photophysics of an expanded hemiporphyrazine: the special case of [30]trithia-2,3,5,10,12,13,15,20,22,23,25,30-dodecaazahexaphyrin

Spectroscopic, crystallographic and electrochemical techniques are applied to characterize the thirty [pi]-electron-expanded hemiporphyrazines synthesized by crossover condensation reaction of 2,5-diamino-1,3,4-thiadiazole and the corresponding phthalonitrile or diiminoisoindoline derivatives. Thirty [pi]-electron-expanded hemiporphyrazines are observed to evolve as broadly absorbing light harvesters with excited state energies of around 2.3 eV that are susceptible to facile one-electron reduction and one-electron oxidation reactions.