Combining electron transfer, spin crossover, and redox properties in metal-organic frameworks.
Livia GetznerDamian PaliwodaLaure VendierLatévi Max Lawson-DakuAurelian RotaruGábor MolnárSaioa CoboAzzedine BousseksouPublished in: Nature communications (2024)
Hofmann coordination polymers (CPs) that couple the well-studied spin transition of the Fe II central ion with electron-responsive ligands provide an innovative strategy toward multifunctional metal-organic frameworks (MOFs). Here, we developed a 2D planar network consisting of metal-cyanide-metal sheets in an unusual coordination mode, brought about by infinitely π-stacked redox-active bipyridinium derivatives as axial ligands. The obtained family of materials show vivid thermochromism attributed to electron transfer and/or electronic spin state change processes that can occur either independently or concomitantly. Importantly, the redox activity of the ligands within the structure leads to the quasi-reversible electrochemical reduction reaction on a spin-crossover complex at solid state. These observations have been confirmed via temperature-dependent single-crystal X-ray diffraction, magnetic measurements, Mössbauer, EPR, optical and vibrational spectroscopies as well as quantum chemical calculations.
Keyphrases
- electron transfer
- metal organic framework
- density functional theory
- solid state
- molecular dynamics
- room temperature
- single molecule
- high resolution
- transition metal
- open label
- molecular dynamics simulations
- placebo controlled
- cancer therapy
- randomized controlled trial
- molecularly imprinted
- gold nanoparticles
- monte carlo
- ionic liquid
- study protocol
- high speed
- network analysis
- aqueous solution