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Substitute group-tuned Schiff-base manganese(III)-based cyanide-bridged bimetallic complexes: synthesis, crystal structures and magnetic properties

Posted on 5. March, 2018.

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The trinuclear cyanide-bridged heterometallic Pd(ii)–Mn(iii) complexes {[Mn(L1)(H2O)]2[Pd(CN)4]} and {[Mn(L2)(H2O)]2[Pd(CN)4]}·2H2O(L1 = N,N′-1,2-propylene-bis(3-methoxysalicylideneiminate; L2 = N,N′-1,2-propylene-bis(3-ethoxysalicylideneiminate) were obtained and structurally and magnetically characterised. X-ray diffraction revealed their cyanide-bridged trinuclear core nature with a conformational difference. The magnetic susceptibilities of the two complexes revealed overall weak antiferromagnetic interactions between the adjacent Mn(iii) ions.

During the past several decades, heterometallic coordination compounds with various functional properties have received intense attention due to their potential applications in high-tech fields. Magnetic complexes attract great research interest not only for the purpose of fully elucidating the nature of magnetic coupling, magneto-structural correlation and some exotic magnetic phenomena, but also for their great underlying application value in the information storage field. As an important molecular magnetism research field, cyanide-bridged magnetic complexes with diverse structure types from discrete polynuclear compounds and one-dimensional chains to two- and three-dimensional networks, whose magnetic exchange interaction occurs through the cyanide bridge, have made great contributions towards examining magneto–structural relationships and clarifying the nature of magnetic coupling.
Among the paramagnetic assembling segments used to prepare cyanide-bridged magnetic complexes, Schiff-base manganese(iii) compounds based on quasi-planar, tetradentate N2O2 salentype ligands (salen = N,N-ethylene-bissalicylideneiminate) have been much studied due to not only their facile synthesis but also, more importantly, their large spin state (S = 2) as well as the usually negative magnetic anisotropy of the central Mn(iii) ions. By using manganese(iii)–salen types of compounds and various polycyanometallates as building blocks, many cyanidebridged magnetic complexes with different structural types and
interesting magnetic properties have been reported. We have prepared and structurally and magnetically investigated some cyanide-bridged M–Mn(iii) (M = Fe, Cr) complexes based on penta- and hexacyanometallates and Schiff-base manganese(iii) compounds containing bicompartmental Schiff-base ligands, and the results indicated that Schiff-base manganese(iii) compounds containing N2O2 and O4 coordination cavities are good candidates for assembling cyanide-bridged heterometallic magnetic complexes.

Read the full article in Journal of Chemical Research, Volume 42, Number 1, January 2018, pp. 28-32


Authors: Jingwen Shia, Yin Zhoua, Chongchong Xuea, Qingyun Liub and Daopeng Zhanga*
aCollege of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, P.R. China
bCollege of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510, P.R. China

Keywords: cyanide-bridged, heterometallic Pt–Mn, Schiff base, crystal structure, magnetic properties

Image: The two Schiff-base manganese compounds used in this study