Hofmann-Like Frameworks Fe(2-methylpyrazine)n[M(CN)2]2 (M = Au, Ag): Spin-Crossover Defined by the Precious Metal
- 17 April 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 59 (9), 6541-6549
- https://doi.org/10.1021/acs.inorgchem.0c00627
Abstract
Hofmann-like cyanometalates constitute a large class of spin-crossover iron(II) complexes with variable switching properties. However, it is not yet clearly understood how the temperature and cooperativity of a spin transition are influenced by their structure. In this paper, we report the synthesis and crystal structures of the metal–organic coordination polymers {FeII(Mepz)[AuI(CN)2]2} ([Au]) and {FeII(Mepz)2[AgI(CN)2]2} ([Ag]), where Mepz = 2-methylpyrazine, along with characterization of their spin-state behavior by variable-temperature SQUID magnetometry and Mössbauer spectroscopy. The compounds are built of cyanoheterometallic layers, which are pillared by the bridging Mepz ligands in [Au] but separated in [Ag]. The complex [Au] exhibits an incomplete stepped spin transition as a function of the temperature with TSCO1 = 170 K and TSCO2 = 308 K for the two subsequent steps. In contrast, the complex [Ag] attains the high-spin state over the whole temperature range. In the crystal structure of [Ag], weak interlayer contacts (Ag−π, Me−π, and Ag–N) are found that may be responsible for an unusual axial elongation of the FeN6 polyhedra. We propose that this structural distortion contributes to the trapping of iron in its high-spin state.Funding Information
- European Commission (734322)
- Ministry of Education and Science of Ukraine (19BF037-01M)
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