Dihydroazulene-buckminsterfullerene conjugates

Article abstract of DOI:10.1021/jo301306y

The dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch has recently attracted interest as a molecular switch for molecular electronics. In this field, Buckminsterfullerene, C₆₀, has been shown to be a useful anchoring group for adhering a molecular wire to an electrode. Here we have combined the two units with the overall aim to elucidate how C₆₀ influences the DHA-VHF switching events. Efficient synthetic protocols for making covalently linked DHA-C₆₀ conjugates were developed, using Prato, Sonogashira, Hay, and Cadiot-Chodkiewicz reactions. These syntheses provide as well a variety of potentially useful DHA and C₆₀ building blocks for acetylenic scaffolding. The two units were separated by bridges of various lengths, such as oligo(phenyleneethynylene) (OPE2 and OPE3) wires. The distance of separation was found to influence strongly the light-induced ring-opening reaction of DHA to its corresponding VHF. Thus, C₆₀ was found to significantly quench this conversion when situated closely to the DHA unit.