Promoting exchange coupling in (CpiPr5)2Gd2X3 complexes

Abstract

Introducing magnetic coupling between lanthanide ions has been shown to yield better-performing single-molecule magnets (SMMs), as exemplified by the Cp₂^iPr₅Ln₂I₃ family of compounds (Cp^iPr₅: pentaisopropylcyclopentadienyl, Ln: Gd, Tb, or Dy). This unique coupling is mediated through an unpaired electron hosted in a σ-like orbital, that results from the two 5d_z² Ln ions, and understanding these interactions holds the key to continue advancing the rational design of SMMs. Here, we focus on the Cp₂^iPr₅Gd₂I₃ spin-only system and apply a recently proposed DFT-based decomposition scheme to assess the chemical and structural factors that affect the magnetic coupling. Based on these, we propose synthetically feasible systems with increased coupling.