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Copper complexes of tripodal ligands have been used as model systems for electron transfer proteins for decades, displaying a broad range of electron self-exchange rates. We herein report a group of six tripodal tetradentate triarylamine ligands which display a varying number of guanidine and 2-methylquinolinyl moieties. Their corresponding Cu(I) complexes have been (re)synthesized and studied with regard to their electron transfer properties. While their molecular structures in the solid state are four-coordinate and display an uncommon umbrella distortion, DFT studies of the Cu(II) systems reveal that they gain an additional ligand in the form of a solvent molecule and exhibit a range of possible conformers that likely co-exist in thermal equilibrium. The redox-couples' electron self-exchange rates were analyzed using Marcus theory and vary over four orders of magnitude which cyclic voltammetry studies suggest to be due to a gated addition-oxidation electron transfer mechanism. This mechanism deviates from previously studied systems, likely due to the structural anomalies of the Cu(I) systems. This demonstrates that the chosen path of tripodal model systems can be influenced by molecular design. [ABSTRACT FROM AUTHOR]

Keywords: alcoholysis; chemical recycling; circular (bio)economy; homogeneous catalysis; poly(lactic acid) EN alcoholysis chemical recycling circular (bio)economy homogeneous catalysis poly(lactic acid) 1 1 1 05/27/22 20220501 NES 220501 B The cover feature image shows b that zinc guanidine complexes act with the yin-yang principle for bioplastics: they are able to promote the controlled ring-opening polymerisation of lactide to polylactide under industrial conditions but also the recycling of polylactide into lactates which go back into the value chain. Alcoholysis, chemical recycling, circular (bio)economy, homogeneous catalysis, poly(lactic acid). [Extracted from the article]