M. Moors, J. Warneke, X. López, C. de Graaf, B. Abel, K. Y. Monakhov
Acc. Chem. Res. 2021, 54, 3377–3389
https://pubs.acs.org/doi/10.1021/acs.accounts.1c00311

This Account highlights recent experimental and theoretical work focusing on the development of polyoxometalates (POMs) as possible active switching units in what may be called “molecule-based memory cells”. Herein, we critically discuss how multiply charged vanadium-containing POMs, which exhibit stable metal–oxo bonds and are characterized by the excellent ability to change their redox states without significant structural distortions of the central polyoxoanion core, can be immobilized best and how they may work optimally at appropriate surfaces. Furthermore, we critically discuss important issues and challenges on the long way toward POM-based nanoelectronics. This Account is divided into four sections shedding light on POM interplay in solution and on surfaces, ion soft-landing of mass-selected POMs on surfaces, electronic modification of POMs on surfaces, and computational modeling of POMs on surfaces. The sections showcase the complex nature of far-reaching POM interactions with the chemical surroundings in solution and the properties of POMs in the macroscopic environment of electrode surfaces. Section 2 describes complex relationships of POMs with their counter-cations, solvent molecules, and water impurities, which have been shown to exhibit a direct impact on the resulting surface morphology, where a concentration-dependent formation of micellar structures can be potentially observed. Section 3 gives insights into the ion soft-landing deposition of mass-selected POMs on electrode surfaces, which emerges as an appealing method because the simultaneous deposition of agglomeration-stimulating counter-cations can be avoided. Section 4 provides details of electronic properties of POMs and their modification by external electronic stimuli toward the development of multiple-state resistive (memristive) switches. Section 5 sheds light on issues of the determination of the electronic structure properties of POMs across their interfaces, which is difficult to address by experiment. The studies summarized in these four sections have employed various X-ray-scattering, microscopy, spectroscopy, and computational techniques for imaging of POM interfaces in solution and on surfaces to determine the adsorption type, agglomeration tendency, distribution, and oxidation state of deposited molecules. The presented research findings and conceptual ideas may assist experimentalists and theoreticians to advance the exploration of POM electrical conductivity as a function of metal redox and spin states and to pave the way for a realization of (“brain-inspired”) POM-based memory devices, memristive POM-surface device engineering, and energy efficient nonvolatile data storage and processing technologies.

R. Pütt, P. Kozłowski, I. Werner, J. Griebel, S. Schmitz, J. Warneke, K. Y. Monakhov
Inorg. Chem. 2021, 60, 80–86
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02257

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.