{P₂V₃W₁₅}-Polyoxometalates Functionalized with Phthalocyaninato Y and Yb Moieties

A tris(alkoxo)pyridine-augmented Wells-Dawson polyoxometalate (nBu₄N)₆[WD-Py] (WD = P₂V₃W₁₅O₅₉(OCH₂)₃C, Py = C₅H₄N) was functionalized with phthalocyaninato metal moieties (MPc where M = Y or Yb and Pc = C₃₂H₁₆N₈) to afford (nBu₄N)₄[HWD-Py(MPc)] compounds. High-resolution mass spectrometry was used to detect and identify the hybrid assembly. The magnetism studies reveal substantial differences between M = Yb (monomeric, single-ion paramagnetism) and M = Y (containing dimers, radical character). The results of electronic paramagnetic resonance spectroscopy, SQUID magnetometry, and magnetochemical calculations indicate the presence of intramolecular charge transfer from the MPc moiety to the polyoxometalate and of intermolecular charge transfer from the MPc moiety of one molecule to the polyoxometalate unit of another molecule. These compounds with identified V^IV ions represent unique examples of transition-metal/lanthanide complex-POM hybrid compounds with nonphotoinduced charge transfer between electron donor and acceptor centers.