Supramolecular Functionalization of Carbon Nano-Cluster with π-Conjugated Host Molecules

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A methylrhodium(III) porphyrin cyclic dimer was found to form supramolecular oscillators with fullerene homo and hetero dimers such as C_<120> and C_<130>, where included fullerenes oscillate back and forth within the porphyrin dimer iso- and anisotropically, respectively, without dissociation. From thermodynamic analysis of the oscillation processes via simulation of VT-NMR spectral profiles of the complexes and saturation transfer experiments, these oscillations are found to be entropy-driven and retarded by the solvent-fullerene interactions.From SQUID and 2D-ESR measurements, ferromagnetic coupling of spins between paramagnetic copper porphyrin cyclic dimers and La@C_<82> was found upon complextaion of the host and guest molecules, while the dimer alone or with diamagnetic C_<60> does not show any interaction of the spins at the host molecules.