Structurally Flexible and Solution Stable [Ln 4 TM 8 (OH) 8 (L) 8 (O 2 CR) 8 (MeOH) y ](ClO 4 ) 4 : A Playground for Magnetic Refrigeration.

The family of compounds of general formula [LnIII 4 TMII 8 (OH)8 (L)8 (O2 CR)8 (MeOH)y ](ClO4 )4 {[Gd4 Zn8 (OH)8 (hmp)8 (O2 Ci Pr)8 ](ClO4 )4 (1a); [Y4 Zn8 (OH)8 (hmp)8 (O2 Ci Pr)8 ](ClO4 )4 (1b); [Gd4 Cu8 (OH)8 (hmp)8 (O2 Ci Pr)8 ](ClO4 )4 (2a); [Y4 Cu8 (OH)8 (hmp)8 (O2 Ci Pr)8 ](ClO4 )4 (2b); [Gd4 Cu8 (OH)8 (hep)8 (O2 Ci Pr)8 ](ClO4 )4 (3a); [Gd4 Cu8 (OH)8 (Hpdm)8 (O2 Ct Bu)8 ](ClO4 )4 (4a); [Gd4 Cu8 (OH)8 (ea)8 (O2 CMe)8 ](ClO4 )4 (5a); [Gd4 Ni8 (OH)8 (hmp)8 (O2 CEt)8 (MeOH)6 ](ClO4 )4 (6a); [Y4 Ni8 (OH)8 (hmp)8 (O2 CEt)8 (MeOH)6 ](ClO4 )4 (6b); [Gd4 Co8 (OH)8 (hmp)8 (O2 CEt)8 (MeOH)6 ](ClO4 )4 (7a); [Y4 Co8 (OH)8 (hmp)8 (O2 CEt)8 (MeOH)6 ](ClO4 )4 (7b)} can be formed very simply and in high yields from the reaction of Ln(NO3 )3 ·6H2 O and TM(ClO4 )2 ·6H2 O and the appropriate ligand blend in a mixture of CH2 Cl2 and MeOH in the presence of a suitable base. Remarkably, almost all the constituent parts, namely the lanthanide (or rare earth) ions LnIII (here Ln = Gd or Y), the transition metal ions TMII (here TM = Zn, Cu, Ni, Co), the bridging ligand L (Hhmp = 2-(hydroxymethyl)pyridine; Hhep = 2-(hydroxyethyl)pyridine; H2 pdm = pyridine-2,6-dimethanol; Hea = 2-ethanolamine), and the carboxylates can be exchanged while maintaining the structural integrity of the molecule. NMR spectroscopy of diamagnetic complex 1b reveals the complex to be fully intact in solution with all signals from the hydroxide, ligand L, and the carboxylates equivalent on the NMR time scale, suggesting the complex possesses greater symmetry in solution than in the solid state. High resolution nano-ESI mass spectrometry on dichloromethane solutions of 2a and 2b shows both complexes are present in two charge states with little fragmentation; with the most intense peak in each spectrum corresponding to [Ln4 Cu8 (OH)8 (hmp)8 (O2 Ci Pr)8 ](ClO4 )2 2+ . This family of compounds offers an excellent playground for probing how the magnetocaloric effect evolves by introducing either antiferromagnetic or ferromagnetic interactions, or magnetic anisotropy, by substituting the nonmagnetic ZnII (1a) with CuII (2a), NiII (6a) or CoII (7a), respectively. The largest magnetocaloric effect is found for the ferromagnetically coupled complex 6a, while the predominant antiferromagnetic interactions in 2a yield an inverse magnetocaloric effect; that is, the temperature increases on lowering the applied field, under the proper experimental conditions. In spite of increasing the magnetic density by adding ions that bring in antiferromagnetic interactions (2a) or magnetic anisotropy (7a), the magnetocaloric effect is overall smaller in 2a and 7a than in 1a, where only four GdIII spins per molecule contribute to the magnetocaloric properties.