Issue 3, 2014

Trinuclear heterometallic CuII–MnII complexes of a salen type Schiff base ligand: anion dependent variation of phenoxido bridging angles and magnetic coupling

Abstract

Five new trinuclear heterometallic CuII–MnII complexes [(CuL)2Mn(O2CPh)2] (1), [(CuL)2Mn(N3)2] (2), [(CuL)2Mn(NCO)2] (3), [(CuL)2Mn(NO3)2] (4) and [(CuL)2Mn(Sal)2]·CH2Cl2 (5) have been synthesized with the di-Schiff base ligand H2L (where H2L = N,N′-bis(salicylidene)-1,3-propanediamine and Sal = salicylate). These complexes with different anionic co-ligands have been synthesized to attain a large variation in phenoxido bridging angles and to investigate its consequence on magnetic properties. Single crystal X-ray diffraction analyses reveal that complexes 1, 2, 4 and 5 are linear, whereas 3 has an angular geometry. Variable temperature magnetic susceptibility measurements suggest that all five complexes possess an overall antiferromagnetic interaction between CuII and MnII ions, which results in a final ferrimagnetic ground state with spin 3/2 in the CuII–MnII–CuII trinuclear structure. The weakest antiferromagnetic interaction (JCu–Mn = −7.0 cm−1) is observed for 2 having the lowest value of the Cu–O–Mn angle (92.0°), while the strongest antiferromagnetic interaction (JCu–Mn = −26.5 cm−1) is observed for 3 having the largest Cu–O–Mn angle (101.4°). Complexes 1, 4 and 5 show average Cu–O–Mn angles of 98.2°, 97.6° and 97.7°, respectively, that lead to intermediate antiferromagnetic interactions (JCu–Mn = −9.6, −9.7, −9.3 cm−1 respectively).

Graphical abstract: Trinuclear heterometallic CuII–MnII complexes of a salen type Schiff base ligand: anion dependent variation of phenoxido bridging angles and magnetic coupling

Supplementary files

Article information

Article type
Paper
Submitted
25 Jul 2013
Accepted
06 Oct 2013
First published
08 Oct 2013

Dalton Trans., 2014,43, 990-998

Trinuclear heterometallic CuII–MnII complexes of a salen type Schiff base ligand: anion dependent variation of phenoxido bridging angles and magnetic coupling

P. Seth, S. Ghosh, A. Figuerola and A. Ghosh, Dalton Trans., 2014, 43, 990 DOI: 10.1039/C3DT52012A

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