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Issue 2, 2012
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Synthesis of the first heterometalic star-shaped oxido-bridged MnCu3 complex and its conversion into trinuclear species modulated by pseudohalides (N3, NCS and NCO): Structural analyses and magnetic properties

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Abstract

A tetra-nuclear, star-shaped hetero-metallic copper(II)–manganese(II) complex, [{CuL(H2O)}2(CuL)Mn](ClO4)2 (1) has been synthesized by reacting the “complex as ligand” [CuL] with Mn(ClO4)2 where H2L is the tetradentate di-Schiff base derived from 1,3-propanediamine and 2-hydroxyacetophenone. Upon treatment with the polyatomic anions azide, cyanate, or thiocyanate in methanol medium, complex 1 transforms into the corresponding trinuclear species [(CuL)2Mn(N3)2] (2), [(CuL)2Mn(NCO)2] (3) and [(CuL)2Mn(NCS)2] (4). All four complexes have been structurally and magnetically characterized. In complex 1 the central Mn(II) ion is encapsulated by three terminal [CuL] units through the formation of double phenoxido bridges between Mn(II) and each Cu(II). In complexes 2–4 one of the CuL units is replaced by a couple of terminal azide, N-bonded cyanate or N-bonded thiocyanate ions respectively and the central Mn(II) ion is connected to two terminal Cu(II) ions through a double asymmetric phenoxido bridge. Variable temperature magnetic susceptibility measurements show the presence of moderate ferrimagnetic exchange interactions in all the cases mediated through the double phenoxido bridges with J values (H = −JSiSi + 1) of −41.2, −39.8 and −12.6 cm−1 (or −40.5 and −12.7 cm−1 if we use a model with two different exchange coupling constants) for the tetranuclear MnCu3 cluster in compound 1 and −20.0, −17.3 and −32.5 cm−1 for the symmetric trinuclear MnCu2 compounds 2–4. These ferrimagnetic interactions lead to spin ground states of 1 (5/2 − 3*1/2) for compound 1 and 3/2 (5/2 − 2*1/2) for compounds 2–4.

Graphical abstract: Synthesis of the first heterometalic star-shaped oxido-bridged MnCu3 complex and its conversion into trinuclear species modulated by pseudohalides (N3−, NCS− and NCO−): Structural analyses and magnetic properties

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Supplementary files

Article information


Submitted
14 Jul 2011
Accepted
21 Sep 2011
First published
31 Oct 2011

Dalton Trans., 2012,41, 462-473
Article type
Paper

Synthesis of the first heterometalic star-shaped oxido-bridged MnCu3 complex and its conversion into trinuclear species modulated by pseudohalides (N3, NCS and NCO): Structural analyses and magnetic properties

S. Biswas, S. Naiya, C. J. Gómez-García and A. Ghosh, Dalton Trans., 2012, 41, 462
DOI: 10.1039/C1DT11333J

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