Structure and magnetic properties of two cyanide-bridged one-dimensional M–CuII (M = FeIII or FeII) bimetallic assemblies from ferricyanide and CuN42+ (N4 = 1,4,8,11-tetraazacyclotetradecane and N,N ′-bis(2-pyridylmethylene)-1,3-propanediamine) building blocks
- 1 February 2000
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 4,p. 505-509
- https://doi.org/10.1039/a908485a
Abstract
Two bimetallic assemblies K[Cu(cyclam)][Fe(CN)6]·4H2O 1 and [Cu(L)][Cu(L1)][Fe(CN)6]·6.5H2O 2 (cyclam = 1,4,8,11-tetraazacyclotetradecane; L = N,N′-bis(2-pyridylmethylene)-1,3-propanediamine and L1 = N-2-pyridylmethylene-1,3-propanediamine) have been prepared from the reaction of [Fe(CN)6]3− and the precursors [Cu(cyclam)]2+ and [Cu(L)]2+, respectively, and their structure and magnetic properties studied. The structure of 1 consists of polymeric zigzag chains of alternating [Fe(CN)6]3− and [Cu(cyclam)]2+ units, K+ cations and crystal water molecules. In the crystals the chains are linked by CN–K–NC interactions, to form a two-dimensional layer structure. Magnetic measurements show a weak ferromagnetic intrachain interaction based on the strict orthogonality of the magnetic orbitals of the FeIII and CuII. In the structure of 2 each [Cu(L1)]2+ unit is bonded to centrosymmetric [Fe(CN)6]4− and [Cu(L)Fe(CN)6Cu(L)] units through two cis bridging cyanide ligands. Owing to the symmetry, a unique one-dimensional zigzag chain structure is formed through trans bridging cyanide ligands of the two crystallographically non-equivalent [Fe(CN)6]4− groups. In the course of the reaction the [Fe(CN)6]3− ion undergoes a reduction to [Fe(CN)6]4− whereas the [Cu(L)]2+ ion partly hydrolyses to [Cu(L1)]2+. Compound 2 is essentially paramagnetic within the chain.Keywords
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