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Two new fullerodendrimers, with two and four ferrocene units on their periphery, have been synthesized by 1,3-dipolar cycloaddition reactions between the corresponding azomethine ylides and C(60). These new compounds have been studied by using cyclic voltammetry and UV/Vis spectroscopy. Weak intramolecular interactions between the fullerene cage and the ferrocene groups have been found. The photochemical events of both fullerene-ferrocene dendrimers have been probed by means of steady-state and time-resolved techniques. The steady-state emission intensities of the fulleropyrrolidine-ferrocene dendrimers 1 and 2 were found to be quenched relative to the N-methylfulleropyrrolidine without substituents that was used as a model. The nanosecond transient absorption spectral studies revealed efficient charge separation in both systems, even in toluene. The lifetimes of the (C(60))(*-)-(dendron)(*+) are higher for the second-generation fullerodendrimer (with four ferrocene units) and they are of the order of tens of nanoseconds in toluene and hundreds of nanoseconds in polar solvents.

Two novel ruthenocene-C 60 dyads, with a 2-pyrazoline ring or a pyrrolidine ring as a linker, have been synthesized with the aim of providing a simple model of natural photosynthesis. The photophysical properties of the two ruthenocene-C 60 dyads have been investigated by steady-state absorption and fluorescence, time-resolved fluorescence and nanosecond transient measurements in polar and non-polar solvents. The charge separation takes place in the ruthenocenepyrazolino[60]fullerene more efficiently than in the ruthenocene-pyrrolidino[60]fullerene dyad. The lifetimes of the charge-separated states of the ruthenocene-pyrazolino[60]fullerene and the ruthenocene-pyrrolidino[60]fullerene dyads are 100 ns in PhCN. It was found that the ruthenocene-[60]fullerenes have an ability to prolong the charge-separated states compared with those for ferrocene-[60]fullerenes.

Owing to their bioorthogonality, transition metals have become very popular in the development of biocompatible bond‐cleavage reactions. However, many approaches require design and synthesis of complex ligands or formulation of nanoparticles which often perform poorly in living cells. This work reports on a method for the generation of an active palladium species that triggers bond‐cleaving reactions inside living cells. We utilized the water‐soluble Na2PdCl4 as a simple source of PdII which can be intracellularly reduced by sodium ascorbate to the active Pd0 species. Once generated, Pd0 triggers the cleavage of allyl ether and carbamate caging groups leading to the release of biologically active molecules. These findings do not only expand the toolbox of available bioorthogonal dissociative reactions but also provide an additional strategy for controlling the reactivity of Pd species involved in Pd‐mediated bioorthogonal reactions.