S/Se-Terchalcogenophene-C(60) Dyads: Synthesis and Characterization of Optical and Photosensitizing Properties

Fullerenes have been long investigated for application as singlet oxygen sources. Even though they possess high photosensitizing efficiency, their practical use is still limited, mostly because of insufficient absorption of visible and/or near-infrared light. This limitation can be overcome by introducing organic chromophores that absorb longer-wavelength light, either by covalent attachment to C(60) or by its encapsulation in a polymeric matrix. In this work, we investigated the photosensitizing properties of the C(60) molecule functionalized with organic units comprising thiophene or selenophene rings. The chemical structures of the synthesized dyads were characterized by nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. The influence of the S/Se atoms and vinyl linkage between the organic unit and C(60) on the absorptive and emissive properties of the dyads was investigated and correlated with their photosensitizing activity. For the latter, we used a standard chemical singlet oxygen trap. A selected dyad C(60)ThSe(2) was also applied as a source of singlet oxygen in a model photocatalyzed synthesis of the fine chemical juglone from 1,5-dihydroxynapthalene.