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Abstract. In magnetic compounds with Jahn-Teller (JT) ions (such as Mn 3+ or Cu 2+ ), the ordering of the electron or hole orbitals is associated with cooperative lattice distortions. There the role of JT effect, although widely recognised, is still elusive in the ground state properties. We suggest that, in these materials, there exist elementary excitations whose energy spectrum is described in terms of the total angular momentum eigenstates and is quantised as in quantum rotors found in JT centers. We observed features originating from these excitations in the optical spectra of a model compound LaMnO 3 using ellipsometry technique. They appear clearly as narrow sidebands accompanying the electron transition between the JT split orbitals on neighbouring Mn 3+ ions, strongly influenced by anisotropic spin correlations. We present these results together with new experimental data on photoluminescence and its kinetics found in LaMnO 3 , which lend additional support to the ellipsometry implying the existence of the quantum rotor orbital excitations. We note that the discovered elementary excitations of quantum rotors may play an important role in many unusual properties observed in these materials upon doping, such as hightemperature superconductivity and colossal magnetoresistance.

The methylpyropheophorbide-fullerene[60] dyad was synthesized by 1,3-dipolar cycloadditions of the corresponding azomethine ylide to C 60 (Prato reaction). Using the mass spectrometric method with soft matrix-activated ionization it was possible to achieve a significant reduction in fragmentation processes by the retro-Diels-Alder reaction, which allows to reliably detect the presence of polyadducts of azomethine ylide cycloadditions to fullerene. The use of gel permeation chromatography under conditions of weakening of the intermolecular π-π interaction between methylpyropheophorbide and fullerene moieties makes it possible to effectively separate mixed products with ~ 1.5 fold difference in molecular weight. It has been shown that the fluorescence of the dyad is quenched more than 5000 times (compared to the native dye). The singlet oxygen quantum yield of the dyad is 360 times less than that for the native methylpyropheophorbide a, however, its efficiency of superoxide generation increases by 18.5 times. The obtained result agrees well with the previously reported mechanism of relaxation of the excited state of the dyad through a charge-separated state, which can lead to the formation of superoxide. The observed effects indicate a change in the mechanism of photodynamic activity from type II (generation of singlet oxygen) for the native dye to type I (generation of superoxide) for the dyad, which shows a promising method of creation of highly efficient photosensitizers based on similar dye-fullerene[60] dyads.

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Here we report the investigation of photophysical properties and photodynamic action of two novel water soluble hybrid molecular structures based on [60]fullerene dyads bearing covalently attached residues of anthracycline antibiotic "ruboxyl". Molecular structures of the designed compounds were confirmed by IR and UV-VIS absorption spectroscopy, electrospray mass spectrometry (compound 5), and (1)H and (13)C NMR spectroscopy. Dynamic light scattering, steady-state and kinetic fluorimetry and UV-VIS absorption spectroscopy techniques were used to study the behavior of the synthesized hybrid molecular structures in aqueous solutions. Photodynamic activity of the compounds was evaluated by monitoring the O2(-) generation under visible light irradiation using the NBT test. It has been shown that the anthracycline chromophore (ruboxyl moiety possesses no photodynamic activity) behaves as an efficient photosensitizer for the fullerene core operating via the energy and/or the electron transfer pathways. The presented approach opens up wide opportunities for the design of various fullerene-based donor-acceptor systems with enhanced photodynamic properties potentially suitable for biomedicinal applications.

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