Macrocycles with and without B-N bonds were prepared from reaction of C6F5BH2·SMe2 or MesBH2 with the 2,6-pyridinedimethanol derivatives. Both classes of macrocycle reacted with B(C6F5)3 but were unreactive to small molecules. These observations provide insights for the subsequent design of macrocyclic FLPs for multi-electron reactions.