Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna–C60 contact and effective photodynamic potential

We report the synthesis of a new class of photoresponsive C(60)-DCE-diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C(60)(>DPAF-C(n)) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C(60)(>CPAF-C(n)) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C(60)-DCE-DPAF nanostructures to longer red wavelengths than C(60)(>DPAF-C(n)). Accordingly, C(60)(>CPAF-C(n)) may allow 2γ-PDT using a light wavelength of 1000-1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C(60)(>DPAF-C(2) (M)) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the (1)O(2) quantum yield of C(60)(>CPAF-C(2) (M)) was found to be nearly 6-fold higher than that of C(60)(>DPAF-C(2) (M)), demonstrating the large light-harvesting enhancement of the CPAF-C(2) (M) moiety and leading to more efficient triplet state generation of the C(60)> cage moiety. This led to highly effective killing of HeLa cells by C(60)(>CPAF-C(2) (M)) via photodynamic therapy (200 J cm(-2) white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group.