1,2,3-Triazole-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV), and related compounds: ground state spins ranging from S = 0 to 25 and spin-enhanced magnetocaloric effect.

We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe)18-Cl6] (M ) FeIII, CrIII) and [V14(L)6O6(OMe)18Cl6-xOx] (L ) anion of 1,2,3-triazole or derivative). Crystal structuredata are reported for the {M14} complexes [Fe14(C2H2N3)6O6(OMe)18Cl6], [Cr14(bta)6O6(OMe)18Cl6] (btaH )benzotriazole), [V14O6(Me2bta)6(OMe)18Cl6-xOx] [Me2btaH ) 5,6-Me2-benzotriazole; eight metal sites are VIII, theremainder are disordered between {VIII-Cl}2+ and {VIVdO}2+] and for the distorted [FeIII14O9(OH)(OMe)8(bta)7-(MeOH)5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance oftemperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronicspins of S e 25, among the highest known, while in contrast the {Cr14} complex has an S ) 0 ground statedespite having a very similar structure and all complexes being dominated by intramolecular antiferromagneticexchange interactions. The {Fe14} complexes undergo a magnetic phase transition to long-range ordering at relativelyhigh temperatures for molecular species, which are governed by the steric bulk of the triazole (TN ) 1.8 and 3.4K for L ) bta- and H2C2N3-, respectively). The huge spins of the {Fe14} complexes lead to very large magnetocaloriceffects (MCE)sthe largest known for any material below 10 Kswhich is further enhanced by spin frustration withinthe molecules due to the competing antiferromagnetic interactions. The largest MCE is found for [Fe14-(C2H2N3)6O6(OMe)18Cl6] with an isothermal magnetic entropy change -¢Sm of 20.3 J kg-1 K-1 at 6 K for anapplied magnetic field change of 0-7 T.