The First Series of Heterometallic LnIII‐VIV Complexes Based on Substituted Malonic Acid Anions: Synthesis, Structure and Magnetic Properties.

The reaction of VOSO4 with K2cbdc (cbdc2– is cyclobutane‐1,1‐dicarboxylate anion) and Ln(NO3)3 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu) yielded 17 novel heterometallic LnIII‐VIV compounds comprising stable bis‐chelate units {VIVO(cbdc)2(H2O)}. Three structural types of compounds are formed depending on the nature of the rare‐earth metal: 1D polymers {[Ln(VO)(cbdc)2(H2O)7]·0.5[VO(cbdc)2]}n (structural type I) [Ln = La (1), Ce (2)], 3D polymers {[KLn(VO)2(cbdc)4(H2O)9]·3.5H2O}n (structural type II) [Ln = La (3), Ce (4), Pr (5), Nd (6), Sm (7), Eu (8), Gd (9), Tb (10), Dy (11), Ho (12)] comprising trinuclear units {LnV2}, and octanuclear complexes {[KLn(VO)2(cbdc)4(H2O)11]·2H2O}2 (structural type III) [Ln = Y (13), Er (14), Tm (15), Yb (16), Lu (17)] containing dinuclear units {LnV}. Magnetic properties were investigated for all isolated compounds. The GdIII‐VIV compound has ferromagnetic and antiferromagnetic exchange interactions between isotropic VIV and GdIII ions. Calculations using the DFT method at the UB3LYP/6‐31G(d,p)/SDD level of theory were performed in order to explain the different nature of exchange interactions in two GdIII‐VIV pairs. The YbIII‐VIV complex displays single‐molecule magnet properties; the effective energy barrier was estimated at ΔEeff/kB = 26 K. The magnetic properties of LnIII‐VIV compounds with heavy lanthanide ions (LnIII = Er, Tm, Yb) were rationalized in terms of crystal‐field calculations for LnIII ions. Three structural types of heterometallic LnIII‐VIV substituted malonates were synthesized from the bis‐malonate vanadyl unit and were characterized by single‐crystal and powder XRD and by magnetic measurements. The structures of the new compounds depend on the nature of the rare‐earth metal: a decrease in the LnIII ionic radius is accompanied by a decrease in the nuclearity of the {LnIII‐VIV} unit. [ABSTRACT FROM AUTHOR]