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Inducing ring distortions in unsubstituted metallophthalocyanines using axial N-heterocyclic carbenes

Abstract

A series of metallophthalocyanine (PcM) complexes with axial N-heterocyclic carbene ligands (NHC; 1,3-diisopropylimidazol-2-ylidene (DIP) and 1,3-dimethylbenzimidazol-2-ylidene (DMB)) were prepared and structurally characterized. PcCoII(DIP), PcZnII(DIP), and PcZnII(DMB) are five-coordinate complexes with mild dome-type Pc-ring distortions, while PcFeII(DIP)2 is six-coordinate and has a very large ruffle-type ring-distortion with respect to typical PcM(L)2 systems. The distortion is induced by the highly steric axial DIP ligands. The distortions were quantified and classified by their bond lengths and torsion angles, and according to the normal-coordinate structural decomposition (NSD) analysis. Upon ligation of the NHC, the insoluble PcM materials were solublized in common organic solvents, with typical UV-visible Q-band maxima observable between 658 and 677 nm; the increased solubility is rationalized in terms of the reduced solid-state aggregation of the complexes, attributable to the axial ligation. Ring-unsubstituted metallophthalocyanines with N-heterocyclic carbenes are soluble in a variety of solvents. The axial NHC ligands generate ruffle and dome-type distorted Pc-rings, with very prominent deformations in the di-axially substituted PcFeII.

article Article
date_range 2024
language English
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