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In this report, the use of nitroxide radicals in the field of supramolecular chemistry and how electron paramagnetic resonance (EPR) has been used for detecting and identifying supramolecular assemblies are briefly reviewed. Selected examples are reported, including the synthesis of open shell mechanically interlocked molecules (MIMs) such as rotaxanes, in which the dumbbell, the wheel or both are tagged with nitroxide radicals.

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