Heterobimetallic 3d-4f complexes supported by a Schiff-base tripodal ligand

Abstract

Complexes featuring multiple metal centres are of growing interest regarding metal-metal cooperation and its tuneability. Here the synthesis and characterisation of heterobimetallic complexes of a 3d metal (3: Mn, 4: Co) and lanthanum supported by a (1,1,1-tris[(3-methoxysalicylideneamino)methyl]ethane) ligand is reported, as well as discussion of their electronic strucure via EPR spectroscopy, electrochemical experiments and computational studies. Competitive binding experiments of the ligand and various metal salts unequivocally demonstrate that in these heterobimetallic complexes the 3d metal (Mn, Co) selectively occupies the κ6-N3O3 binding site of the ligand, whilst La occupies the κ6-O6 metal binding site in line with its relative oxophilicity. Electron paramagnetic resonance spectroscopy supported by density functional theory analysis indicates that the 3d metal is high spin in both cases (S = 5/2 (Mn), 3/2 (Co)). Cyclic voltammetry studies on the Mn/La and Co/La bimetallic complexes revealed a quasi-reversible Mn2+/3+ redox process and poorly-defined irreverisble oxidation events respectively.

Supplementary files

Article information

Article type
Paper
Submitted
10 Nov 2023
Accepted
29 Apr 2024
First published
30 Apr 2024
This article is Open Access
Creative Commons BY license

Dalton Trans., 2024, Accepted Manuscript

Heterobimetallic 3d-4f complexes supported by a Schiff-base tripodal ligand

R. A. Musgrave, B. C. Thompson, D. Graycon, D. Hebron, T. Neumann, M. Roessler, A. Collauto and D. Wilson, Dalton Trans., 2024, Accepted Manuscript , DOI: 10.1039/D3DT03760F

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