Magnetic interactions controlled by light in the family of Fe(II)-M(IV) (M = Mo, W, Nb) hybrid organic-inorganic frameworks

Michał Magott; Magdalena Ceglarska; Michał Rams; Barbara Sieklucka; Dawid Pinkowicz

doi:10.1039/d2dt00777k

Magnetic interactions controlled by light in the family of Fe(II)-M(IV) (M = Mo, W, Nb) hybrid organic-inorganic frameworks

Dalton Trans. 2022 Jun 7;51(22):8885-8892. doi: 10.1039/d2dt00777k.

Authors

Michał Magott¹, Magdalena Ceglarska², Michał Rams², Barbara Sieklucka¹, Dawid Pinkowicz¹

Affiliations

¹ Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, Poland. michal.magott@uj.edu.pl.
² Jagiellonian University, Institute of Physics, Łojasiewicza 11, 30-348 Kraków, Poland.

PMID: 35635098
DOI: 10.1039/d2dt00777k

Abstract

Three new hybrid organic-inorganic frameworks employing octacyanidometallates and 4,4'-bypiridine dioxide (4,4'-bpdo) as bridging molecules were prepared and characterized. The three-dimensional coordination frameworks {[Fe^II(μ-4,4'-bpdo)(H₂O)₂]₂[M^IV(CN)₈]·9H₂O}_n (Fe2Mo, Fe2W and Fe2Nb; M = Mo, W and Nb) are composed of cyanido-bridged chains, which are interconnected by the organic linkers. Magnetic measurements for Fe2Nb show a two-step transition to the antiferromagnetic state, which results from the cooperation of antiferromagnetic intra- and inter-chain interactions. Fe2Mo and Fe2W, on the other hand, behave as paramagnets at 2 K because of the diamagnetic character of the corresponding octacyanidometallate(IV) building units. However, after 450 nm light irradiation they show transition to the metastable high spin Mo^IV or W^IV states, respectively, with distinct ferromagnetic intrachain spin interactions, as opposed to the antiferromagnetic ones observed in the Fe2Nb framework.