Combining electron transfer, spin crossover, and redox properties in metal-organic frameworks
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.
Authors
- Latévi Max Lawson Daku (ORCID: https://orcid.org/0000-0003-1305-6807)
- Saioa Cobo (ORCID: https://orcid.org/0000-0002-9353-3417)
- Laure Vendier (ORCID: https://orcid.org/0000-0002-7111-9258)
- Damian Paliwoda (ORCID: https://orcid.org/0000-0003-0020-0515)
- Gábor Molnár (ORCID: https://orcid.org/0000-0001-6032-6393)
- Livia Getzner (ORCID: https://orcid.org/0000-0002-8070-175X)
- Aurelian Rotaru (ORCID: https://orcid.org/0000-0002-8782-7988)
- Azzedine Bousseksou (ORCID: https://orcid.org/0000-0002-1619-532X)
Institutions
- University of Geneva (CH)
- Ştefan cel Mare University of Suceava (RO)
- Centre National de la Recherche Scientifique (FR)
- Université Toulouse III - Paul Sabatier (FR)
- Université Fédérale de Toulouse Midi-Pyrénées (FR)
- Institut National Polytechnique de Toulouse (FR)
- Laboratoire de Chimie de Coordination (FR)
Publication Details
- Journal
- Nature Communications
- Published
- 2024-08-21
- DOI
- https://doi.org/10.1038/s41467-024-51385-8
- Citations
- 23
- Primary Topic
- Magnetism in coordination complexes
- Type
- article
- Field-Weighted Citation Impact
- 2.71
Funders
- European Commission
- Agence Nationale de la Recherche
- Université de Genève
- Unitatea Executiva pentru Finantarea Invatamantului Superior, a Cercetarii, Dezvoltarii si Inovarii