Polyoxoplatinates as covalently dynamic electron sponges and molecular electronics materials

Abstract

In organic systems, dynamic covalent chemistry provides an adaptive approach (i.e., “covalent dynamics”) where thermodynamic equilibria are used to tailor structural and electronic changes in molecular assemblies. The covalent dynamics finds utility in the design of novel self-healing materials, sensors, and actuators. Herein, using density functional theory (DFT) we explore the structural, electronic and transport properties of the Pt-based polyoxometalate (POM) [Pt^III₁₂O₈(SO₄)₁₂]⁴⁻ and its derivatives. The latter POM has six redox responsive {O–Pt–Pt–O} moieties and prospects for storage of up to twelve electrons, thus exemplifying how dynamic covalent chemistry may manifest itself in fully inorganic systems. Simulations of the Au/POM/Au junction show that the electron conduction strongly depends on the redox of the POM but more weakly on its rotations with respect to the Au surface. Moreover, the POM shows promising spin-polarized current behaviour, which can be modulated using bias and gate voltages.