Bulky anion effect on the architecture of chiral dysprosium single‐molecule magnets

The interest for chiral tris(β‐diketonato)lanthanide complexes in coordination chemistry is huge due to its Lewis acid character, optical activity, and the control of the final compound architecture. The reaction of equimolar quantities of [Dy((−)/(+)hfc)(3)(H(2)O)] (hfc(−) = 3‐(heptafluoropropylhydroxymethylene)‐(+/−)‐camphorate) and L led to the formation of a pair of enantiomers for dinuclear complexes [Dy((−)/(+)hfc)(3)(L)](2)⋅C(7)H(16) ([(−)/(+)1]⋅C(7)H(16)) (L = 4′‐(4′′′‐pyridyl‐N‐oxide)‐1,2′:6′1′′‐bis‐(pyrazolyl)pyridine]). Starting from the previous experimental protocol with the addition of bulky BArF anions, a partial dissociation of the chiral [Dy((−)/(+)hfc)(3)(H(2)O)] was observed leading to the isolation of a mono‐dimensional cationic chiral polymer {[Dy((−)/(+)hfc)(2)(L)][BarF]}(n)⋅nCH(3)NO(2) ([(−)/(+)2] ( n )⋅nCH(3)NO(2)). Natural circular dichroism (NCD) highlighted an exciton CD couplet for [(−)/(+)2] ( n ) but not for (−)/(+)1. The latter behaves as a single‐molecule magnet (SMM) with a blocking temperature up to 4 K, whereas [(−)/(+)2] ( n ) is a 1D assembly of field‐induced SMMs with a magnetic relaxation occurring through a Raman process only.