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

Abstract

A tris(alkoxo)pyridine-augmented Wells-Dawson polyoxometalate (<i>n</i>Bu₄N)₆[<b>WD-Py</b>] (WD = P₂V₃W₁₅O₅₉(OCH₂)₃C, Py = C₅H₄N) was functionalized with phthalocyaninato metal moieties (<b>MPc</b> where M = Y or Yb and Pc = C₃₂H₁₆N₈) to afford (<i>n</i>Bu₄N)₄[H<b>WD-Py</b>(<b>MPc</b>)] 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 <i>intra</i>molecular charge transfer from the <b>MPc</b> moiety to the polyoxometalate and of <i>inter</i>molecular charge transfer from the <b>MPc</b> 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.