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Issue 34, 2015
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Syntheses, structures, and magnetic properties of three new cyano-bridged complexes based on the [Mn(CN)6]3− building block

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Abstract

With three pentadentate macrocyclic ligands, three new [Mn(CN)6]3− based complexes, [Mn(LN3O2)(H2O)]2[Mn(CN)6](ClO4)·3H2O (1), {[Mn(LN5)]3[Mn(CN)6]2}n (2) and {[Mn(LN5Me)]3[Mn(CN)6]2}n·10nH2O (3) (LN3O2 = 2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, LN5 = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene, LN5Me = 2,6-bis[1-(2-(N-methylamino)ethylimino)ethyl]-pyridine), have been synthesized and characterized structurally and magnetically. The structure of 1 was found to be a linear MnII2MnIII trinuclear cluster with two MnII capping groups and one MnIII ion connected via two trans-cyano groups. In contrast, compounds 2 and 3 are cyano-bridged 2D networks. Magnetic investigation revealed antiferromagnetic coupling between the MnIII and MnII ions via the bridging cyanide groups. Complex 1 showed paramagnetic behavior down to 2.0 K with no sign of SMM behavior. The magnetic coupling constant of J = −1.63 cm−1 with the Hamiltonian H = −2J(SMn(III)·SMn(II)1 + SMn(III)·SMn(II)2) was obtained from the fitting of the magnetic susceptibility. For 2 and 3, ferrimagnetic ordering was observed with magnetic phase transition temperatures (Tc) being 7.5 K and 7.0 K, respectively. These compounds are rare examples of a small number of [Mn(CN)6]3− based magnetic materials.

Graphical abstract: Syntheses, structures, and magnetic properties of three new cyano-bridged complexes based on the [Mn(CN)6]3− building block

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Supplementary files

Article information


Submitted
06 Jan 2015
Accepted
18 Mar 2015
First published
19 Mar 2015

Dalton Trans., 2015,44, 15189-15197
Article type
Paper
Author version available

Syntheses, structures, and magnetic properties of three new cyano-bridged complexes based on the [Mn(CN)6]3− building block

S. Zhang, X. Zhao and X. Wang, Dalton Trans., 2015, 44, 15189
DOI: 10.1039/C5DT00038F

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