Abstract
New heteroleptic zinc dimeric complexes bearing an aminophenolate ligand of a single-site initiator framework were synthesized and characterized by spectroscopic methods, X-ray analysis, and DFT calculations. The theoretical study, verified by the experimental data, explains the catalytic behaviour in the ROP of lactide in the examined zinc complexes. The presented simple DFT protocol constitutes a valuable method for the qualification of the ancillary ligand to rationally design new complexes to improve their catalytic activity.
Highlights
The synthesis of polymers with programmable by design properties – those suitable for various applications – have attracted significant attention
The ring opening polymerization (ROP) of cyclic esters initiated by metal complexes is the most effective procurement method of PLA among the numerous synthetic procedures studied to date
We published two new zinc examples with aminonaphtholate ancillary ligands, and our results indicated that a sizable group next to the hydroxyl of the aminophenol/aminonaphthol ligands is the reason for the mixture of metal complexes forming.[45]
Summary
The synthesis of polymers with programmable by design properties – those suitable for various applications – have attracted significant attention. The most attractive polymers are those dedicated to nanomedicine, molecular engineering and bio-base active packages.[1,2,3,4,5] Polylactide (PLA) is one of the advanced green polymers, recently commercialized in worldwide production, that has tremendous application potential in the fields of bio-interface materials for surgery, regenerative medicine, tissue engineering, pharmacy, biodegradable packaging and environmentally friendly polymers.[6,7,8,9,10]. The ring opening polymerization (ROP) of cyclic esters initiated by metal complexes is the most effective procurement method of PLA among the numerous synthetic procedures studied to date. The synthesis of well-defined, single-site initiators based on these structural motifs has been the subject of intensively developed studies over the past decade.[11,12,13,14,15] Excellent initiators have been obtained that were supported by di-, tri-
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