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A series of salts comprising cationic manganese(III)-salen complexes and the Tf 2 N anion has been prepared (salen=N,N′-bis(salicylideneaminato)ethylene, Tf 2 N=bis(trifluoromethanesulfonyl)amide) to investigate the effects of axial ligands and substituents on their thermal properties. [Mn(salen)L 2 ][Tf 2 N] (L=H 2 O, pyridine) and their 5-butoxysalen analogs...