Slight ligand modifications within multitopic linear hydroxamates promotes connectivity differences in Cu(ii) 1-D coordination polymers

Abstract

The novel multitopic ligandsN-hydroxy-4-((2-hydroxy-3-methoxybenzyl)amino)benzamide (L₃H₃) andN-hydroxy-4-((2-hydroxybenzyl)amino)benzamide (L₄H₃) have been synthesised through the Schiff base coupling and subsequent reduction of 4-aminophenylhydroxamic acid and eithero-vanillin (to give L₃H₃) or 2-hydroxybenzaldehyde (to give L₄H₃). These linear multitopic ligands bind Cu(ii) centres at both the hydroxamate and phenol ends to form the 1-D coordination polymers [Cu(ii)(L₃H₂)₂]_n(1) and {[Cu(ii)(L₄H₂)₂]·2MeOH}_n(2). Slight differences in the structures of L₃H₃and L₄H₃lead to significant extended connectivity changes upon Cu(ii) metalation that are exampled by a 27% decrease in intra-chain Cu(ii)⋯Cu(ii) distance upon moving from1to2. The significant conformation and metal binding differences shown by L₃H₂⁻and L₄H₂⁻in1and2respectively have been rationalised using density functional theory (DFT) calculations. Hirshfeld surface analysis has been employed to assess and visualise the intra- and intermolecular interactions in both complexes.

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