Hybrid Molecular Magnets with Lanthanide- and Countercation-Mediated Interfacial Electron Transfer between...

A series of {V₁₂}-nuclearity polyoxovanadate cages covalently functionalized with one or sandwiched by two phthalocyaninato (Pc) lanthanide (Ln) moieties via V-O-Ln bonds were prepared and fully characterized for paramagnetic Ln = Sm^III-Er^III and diamagnetic Ln = Lu^III, including Y^III. The LnPc-functionalized {V₁₂O₃₂} cages with fully oxidized vanadium centers in the ground state were isolated as (nBu₄N)₃[HV₁₂O₃₂Cl(LnPc)] and (nBu₄N)₂[HV₁₂O₃₂Cl(LnPc)₂] compounds. As corroborated by a combined experimental (EPR, DC and AC SQUID, laser photolysis transient absorption spectroscopy, and electrochemistry) and computational (DFT, MD, and model Hamiltonian approach) methods, the compounds feature intra- and intermolecular electron transfer that is responsible for a partial reduction at V(3d) centers from V^V to V^IV in the solid state and at high sample concentrations. The effects are generally Ln dependent and are clearly demonstrated for the (nBu₄N)₃[HV₁₂O₃₂Cl(LnPc)] representative with Ln = Lu^III or Dy^III. Intramolecular charge transfer takes place for Ln = Lu^III and occurs from a Pc ligand via the Ln center to the {V₁₂O₃₂} core of the same molecule, whereas for Ln = Dy^III, only intermolecular charge transfer is allowed, which is realized from Pc in one molecule to the {V₁₂O₃₂} core of another molecule usually via the nBu₄N⁺ countercation. For all Ln but Dy^III, two of these phenomena may be present in different proportions. Besides, it is demonstrated that (nBu₄N)₃[HV₁₂O₃₂Cl(DyPc)] is a field-induced single molecule magnet with a maximal relaxation time of the order 10^-3 s. The obtained results open up the way to further exploration and fine-tuning of these three modular molecular nanocomposites regarding tailoring and control of their Ln-dependent charge-separated states (induced by intramolecular transfer) and relaxation dynamics as well as of electron hopping between molecules. This should enable us to realize ultra-sensitive polyoxometalate powered quasi-superconductors, sensors, and data storage/processing materials for quantum technologies and neuromorphic computing.