Grafting Copper and Gallium Corroles onto Zinc Oxide Nanoparticles

Abstract

Two different copper and gallium arylcorroles have been functionalized using the Vilsmeier–Haack reaction. A further Knoevenagel reaction with cyanoacetic acid was performed on both complexes, affording the desired products with yields above 90 %. The newly synthesized compounds have been thoroughly characterized by a combination of spectroscopic methods, optical analyses, and X‐ray crystallography. Moreover, they have been tested as anchoring groups for the hydrothermal synthesis of ZnO nanoparticles. The morphology of the heterogeneous composites has been studied by SEM, EDS and fluorescence microscopy analyses, thus confirming the presence of the corrole macrocycle in the hybrid material.

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

“…Gallium corrole-coated zinc oxide (ZnO) nanoparticles were prepared by the addition of corrole 73 to an ethanol solution of zinc acetate (nanoparticle precursor). Knoevenagel reaction with cyanoacetic acid was used to introduce a monodentate anchoring group into acrolein-substituted gallium corrole complex 72 , leading to the target corrole 73 in high yield (94%) ( Scheme 27 ) [ 68 ]. The presence of the α-cyanocarboxylic group affects the photophysical properties of the corrole 73 , namely, a red-shift was observed in the Soret and Q bands, the fluorescence emission was also redshifted (32 nm) and the fluorescence quantum yield decreased to 2.2%.…”

Synthesis, Spectral, Redox, and Sensing Studies of β-Dicyanovinyl-Appended Corroles and Their Metal Complexes

“…Particular emphasis has been placed on synthesizing π-extended corroles with red-shifted absorption spectra − and improved chemical stability. − In this regard, formylcorroles are diverse starting materials able to be employed in a number of organic reactions such as Wittig olefination, − Knoevenagel condensation, − and cycloaddition − leading to the formation of π-extended corroles. Herein, we report the synthesis of β-DCV-appended corroles (Chart ) from β-formyl precursors.…”

Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

“…The reaction progress and regioselectivity depend on the central metal ion, as copper and silver complexes do not react to the Vilsmeier reagent, whereas (Cor)­Co exhibited high reactivity under similar conditions. The α-cyanocarboxylic group was introduced on 3-acroleyl-appended Ga and 3-formyl ReO corroles using Knoevenagel condensation reaction with cyanoacetic acid under harsh reaction conditions. , …”