Synthesis of Thiophene-Containing Hybrid Calixphyrins of the 5,10-Porphodimethene Type

The synthesis, structure, and optical and electrochemical properties of thiophene-containing hybrid calixphyrins are reported. The 5,10-porphodimethene type 14π- and 16π-S,N2,X-hybrid calixphyrins (X = NH, O, S) were prepared by acid-promoted dehydrative condensation between a thiatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both crystallographic and spectroscopic analyses of the newly prepared hybrid calixphyrins have revealed that the combination of heteroles explicitly influences the electronic structures of the π-conjugated framework. The 14π-S,N2,X-hybrid calixphyrins have proven to be fluorescent in solution.