Tetrathiafulvalene Schiff base Cu(II) 1D coordination polymer upon a metallo-ligand approach

• Published in: Inorganica Chimica Acta Vol. 475; pp. 172 - 176
• Main Authors: Stetsiuk, Oleh, Petrusenko, Svitlana R., El-Ghayoury, Abdelkrim, Kokozay, Vladimir N., Avarvari, Narcis
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 24-04-2018; Elsevier Science Ltd
• Subjects: Chelation; Chemical reactions; Coordination compounds; Coordination polymers; Copper; Copper complexes; Crystal structure; Crystal structure determination; Elongation; Imines; Jahn-Teller effect; Ligands; Metallography; Metals; Phenols; Polymers; Precursors; Schiff base; Single crystals; Solid state; Stoichiometry; Structural analysis; Tetrathiafulvalene; Voltammetry; Schiff base; Coordination polymers; Crystal structure determination; Tetrathiafulvalene; Copper complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2017.09.059

An unprecedented TTF Schiff base ligand containing a pendant hydroxo-ethyl arm provides an one-dimensional Cu(II) coordination polymer as shown by single crystal X-ray analysis.
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•A TTF-salicylaldehyde has been prepared and structurally characterized.•A TTF containing hydroxo-imino-phenol ligand has been prepared.•Formation of a one-dimensional Cu(II) coordination polymer upon a metallo-ligand approach.•All the derivatives are electroactive.
TTF-salicylaldehyde 1 has been prepared by Stille coupling between TTF-SnMe3 and 5-bromo-salicylaldehyde and characterized by single crystal X-ray structure analysis. A set of S⋯S, π-π and donor–acceptor intermolecular interactions is observed in the solid state architecture of this precursor. Its condensation reaction with 2-ethanolamine provided the chelating electroactive ligand 4-TTF-2-((2-hydroxyethyl)iminomethyl)-phenol 2 (H2L1). Reaction with Cu(OAc)2 in a 2:1 stoichiometry afforded the one-dimensional coordination chain-like polymer [Cu(HL1)2]n3 for which the solid state structure has been determined. The Cu(II) coordination sphere contains in the equatorial plane a N2O2 motif arising from two chelating imino-phenol units, while the axial positions are occupied by hydroxo ligands from the pendant hydroxy-ethyl arms of top and bottom neighbouring intra-chain complexes with quite larger Cu–O distances indicative of Jahn-Teller elongation. The TTF units form regular stacks within the chains and further interact laterally through short S⋯S contacts. Cyclic voltammetry measurements on ligand 2 and complex 3 indicate excellent electron donating properties of these multifunctional precursors.