Combining electron transfer, spin crossover, and redox properties in metal-organic frameworks.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39169011.
- Also identified by DOI 10.1038/s41467-024-51385-8 and PMC identifier 11339071.
- Licence recorded as CC BY-NC-ND.
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Abstract
Hofmann coordination polymers (CPs) that couple the well-studied spin transition of the Fe<sup>II</sup> 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.