Modification of the electronic properties of the π-spacer of chromophores linked to calix[4]arene platform for DSSCs applications

Abstract

We have developed two novel dyes based on p-tert-butyl-calix[4]arene in order to evaluate their behavior as sensitizer in photovoltaic devices. These dyes consist in a difunctionalized calix[4]arene with triphenylamine (TPA)-donor, a heteroaromatic π-conjugated spacer, thiophene and benzothiadiazole-phenyl ring, respectively and cyanoacetic acid as acceptor group. The effect of the π-spacer has been studied by UV–vis spectroscopy and Differential Pulse Voltammetry and the models compounds have been theoretically investigated. The dye bearing phenylbenzothiadiazole results in a bathochromic shifted absorption and an adequate efficiency to transfer charge from D to A. The considerable increase of the photocurrent density results in a better efficiency of the devices prepared with these novel dyes with respect to the p-tert-butyl-calix[4]arene derivatives bearing TPA dye. In particular, p-tert-butyl-calix[4]arene derivative based on phenylbenzothiadiazole has reached an efficiency value of 5.84% which means an increase of 33% of the efficiency over those calix[4]arene derivatives with TPA dye.