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The synthesis and characterization of a new member of the pillar[5]arene family carrying a paramagnetic side‐arm based on the 2,2,6,6‐tetramethylpiperidine N‐oxide (TEMPO) moiety has been achieved by the Huisgen‐type CuAAC reaction. The possibility of exploiting the proposed pillar[5]arene as a host in paramagnetic rotaxane‐like structures was tested in the presence of charged guests and confirmed...
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