MnIII-FeIII Heterometallic Compounds within Hydrogen-Bonded Supramolecular Networks Promoted by an [Fe(CN)5(CNH)]2- Building Block: Structural and Magnetic Properties

David Aguilà; Olivier Jeannin; Marc Fourmigué; Ie-Rang Jeon

doi:10.1021/acs.inorgchem.8b00983

Mn^III-Fe^III Heterometallic Compounds within Hydrogen-Bonded Supramolecular Networks Promoted by an [Fe(CN)₅(CNH)]^2- Building Block: Structural and Magnetic Properties

Inorg Chem. 2018 Jul 2;57(13):7892-7903. doi: 10.1021/acs.inorgchem.8b00983. Epub 2018 Jun 12.

Authors

David Aguilà¹, Olivier Jeannin¹, Marc Fourmigué¹, Ie-Rang Jeon¹

Affiliation

¹ Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226 , 35000 Rennes , France.

PMID: 29894171
DOI: 10.1021/acs.inorgchem.8b00983

Abstract

The reaction of [Fe(CN)₆]^3- and [Mn(acacen)]⁺ (H₂acacen = N, N'-bis(acetylacetone)ethylenediamine) building units in the presence of supramolecular cations, [(F-Anil)(18-crown-6)]⁺ (F-Anil⁺ = 3-fluoroanilinium) or [(Me-F-Anil)(18-crown-6)]⁺ (Me-F-Anil⁺ = 3-fluoro-4-methylanilinium), affords two new bimetallic compounds, [(F-Anil)(18-crown-6)][Mn(acacen)Fe(CN)₅(CNH)]·MeOH (1) and [(Me-F-Anil)(18-crown-6)][Mn(acacen)(MeOH)Fe(CN)₅(CNH)]·MeOH (2), respectively. Compound 1 exhibits a one-dimensional topology, while compound 2 is a dinuclear discrete system due to the coordination of a MeOH molecule at the axial position of the [Mn(acacen)]^- unit. For both systems, the acidity of the corresponding supramolecular cation triggers the protonation of the Fe^III moiety as [Fe(CN)₅(CNH)]^2-. Moreover, the resulting -CNH ligand induces hydrogen bonding interactions connecting the chains for 1 or the molecules for 2 into higher dimensional supramolecular networks. Magnetic properties of compounds incorporating these [Fe(CN)₅(CNH)]^2- building blocks were, for the first time, thoroughly investigated, indicating a three-dimensional antiferromagnetic order of single-chain magnets for 1 and an antiferromagnetically interacting S = 3/2 spin ground state for 2.