Direct synthesis of an iron metal-organic framework antiferromagnetic glass

We present a direct route to prepare a family of MOF glasses without a meltable crystalline precursor, in contrast to the conventional melt-quenching approach. This one-step synthesis uses the linker itself as the reaction medium under an inert atmosphere, enabling the incorporation of highly hydrolytically unstable M(II) centers. This route produces high-purity iron (II) MOF glasses avoiding the oxidation and partial degradation commonly associated with the conventional melt-quenching process. The transparent glassy monoliths of formula Fe(im)2–x(bim)x, denoted as dg-MUV-29 (dg = direct-glass), can be prepared with different amounts of imidazole and benzimidazole as well as with linkers with diverse functionalities (NH2, CH3, Br, and Cl). The absence of magnetic impurities allows us to study the magnetic properties of the MOF glass itself and show that MOF glasses are good model systems for topologically-disordered amorphous antiferromagnets. We also present the functional advantages of direct-glass synthesis by creating free-standing films of glassy MOFs and integrating them in optoelectronic devices. Direct-glass synthesis is thus a powerful route to exploit the true functional potential of glassy MOFs, not only realizing further classes of MOF glasses but also unveiling properties that can be accessed with these materials. This work introduces a solvent-free method to directly synthesise MOF glasses without needing a crystalline precursor, enabling device integration, magnetic studies, and functional tuning.