Synthesis, structures, electrochemistry and magnetic properties of a cyano-bridged {Fe2Co2} molecular square

doi:10.1016/j.inoche.2012.04.019

Inorganic Chemistry Communications

Volume 21, July 2012, Pages 84-87

https://doi.org/10.1016/j.inoche.2012.04.019 Get rights and content

Abstract

The reaction of tricyanometallate precursor, (Bu₄N)[(Tp*)Fe(CN)₃] (Tp* = hydrotris(3,5-dimethylpyrazol-l-yl)borate) with Co(ClO₄)₂·6H₂O in the presence of the bidentate dpa (dpa = 2,2′-dipyridyl amine) ligand affords one novel cyano-bridged heterobimetallic {Fe₂Co₂} molecular square, [Fe^III(Tp*)(CN)₃]₂[Co^II(dpa)₂]₂•2ClO₄•4H₂O•4CH₃OH (1). The molecular structure was determined by single-crystal X-ray diffraction. In compound 1, Fe^III ion is coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp* anions. Whereas, the Co^II ion is surrounded by two cyanide nitrogen atoms and four nitrogen atoms from two bidentate dpa ligands. Cyclic voltammetry (CV) measurements showed that complex 1 exhibited one quasi-reversible waves (0.1 V vs SCE) in the reduction process, and irreversible waves in the oxidation process. Magnetic measurements indicate that complex 1 exhibits a strong intramolecular ferromagnetic interaction between the low-spin Fe^III(S = 1/2) and high-spin Co^II(S = 3/2) ions.

Graphical abstract

The reaction of tricyanometallate precursor with Co^II in the presence of the bidentate dpa ligand afford one novel cyano-bridged heterobimetallic {Fe₂Co₂} molecular square. Ferromagnetic properties existed between the metal ions. In addition, the cyclic voltammetry (CV) and magnetic properties of the compound have also been investigated.

Highlights

► One cyano-bridged {Fe₂Co₂} molecular square has been synthesized via rational design. ► Strong ferromagnetic interactions exist between the Fe^III and Co^II ions. ► The compound exhibited quasi-reversible waves in the reduction process. ► The compound exhibited irreversible waves in the oxidation process.

Section snippets

Acknowledgments

This work was partly supported by the NSFC (Grants 21101021 and 91122031) and the Fundamental Research Funds for the Central Universities, China.

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Synthesis, structures, electrochemistry and magnetic properties of a cyano-bridged {Fe2Co2} molecular square

Abstract

Graphical abstract

Highlights

Section snippets

Acknowledgments

Coord. Chem. Rev.

A room-temperature organometallic magnet based on Prussian blue

Nature

Electrochemically tunable magnetic phase transition in a high-Tc chromium cyanide thin film

Science

Photoinduced magnetization with a high Curie temperature and a large coercive field in a cyano-bridged cobalt tungstate bimetallic assembly

J. Am. Chem. Soc.

Photoinduced metal-to-metal charge transfer toward single-chain magnet

J. Am. Chem. Soc.

Single-molecule magnets constructed from cyanometalates: {[Tp*FeIII(CN)3MII(DMF)4]2[OTf]2}·2DMF (MII = Co, Ni)

Inorg. Chem.

An S = 3 cyanide-bridged tetranuclear FeIII2NiII2 square that exhibits slow relaxation of magnetization: synthesis, structure and magnetic properties

Dalton Trans.

Water-switching of spin transitions induced by metal-to-metal charge transfer in a microporous framework

Angew. Chem. Int. Ed.

A Charge-transfer-induced spin transition in a discrete complex: the role of extrinsic factors in stabilizing three electronic isomeric forms of a cyanide-bridged Co/Fe cluster

J. Am. Chem. Soc.

Slow dynamics of the magnetization in one-dimensional coordination polymers: single-chain magnets

Inorg. Chem.

[Fe(bpym)(CN)4]: a new building block for designing single-chain magnets

J. Am. Chem. Soc.

Photoinduced magnetization of a cobalt–iron cyanide

Science

Control of magnetic properties through external stimuli

Angew. Chem. Int. Ed.

Synthesis, structures, electrochemistry and magnetic properties of a cyano-bridged {Fe₂Co₂} molecular square

Electrochemically tunable magnetic phase transition in a high-T_c chromium cyanide thin film

Single-molecule magnets constructed from cyanometalates: {[Tp*Fe^III(CN)₃M^II(DMF)₄]₂[OTf]₂}·2DMF (M^II = Co, Ni)

An S = 3 cyanide-bridged tetranuclear Fe^III₂Ni^II₂ square that exhibits slow relaxation of magnetization: synthesis, structure and magnetic properties

[Fe(bpym)(CN)₄]: a new building block for designing single-chain magnets