Synthesis and Studies of Core-Modified Tellura Dithiasapphyrins.

Abstract

Four different aromatic meso-substituted tellurophene-containing dithiasapphyrins were synthesized by acid-catalyzed [3+2] condensation of 16-telluratripyrrane with bithiophene diol in 22-23% yields. The structural, spectral, and electrochemical properties of tellura dithiasapphyrins were studied and compared with those of previously reported aza (pyrrole)- and other heterocycle (furan, thiophene, and selenophene)-containing dithiasapphyrins. Nuclear magnetic resonance studies indicated that the tellurophene ring in tellura dithiasapphyrins is in the normal conformation, facing toward the inner core, but flips in diprotonated derivatives to an inverted conformation, facing away from the macrocyclic core, unlike aza- and other heterocycle-containing dithiasapphyrins in which pyrrole and the corresponding heterocycle ring always prefer to be in inverted conformation in their neutral and protonated forms. The crystal structure obtained for one of the tellura dithiasapphyrins showed that the macrocycle is highly planar and the tellurophene ring is in the normal conformation. The absorption spectra of tellura dithiasapphyrins exhibited slight hypsochromic shifts compared to those of pyrrole- and other heterocycle-containing dithiasapphyrins. The redox studies indicated that the tellura dithiasapphyrins are electron deficient and readily undergoes reductions. Density functional theory and nuclear independent chemical shift studies indicated that the macrocycles are aromatic, and the computational results closely matched the experimental observations.