Abstract
A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This A-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable A-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.
Highlights
Phthalocyanines and porphyrins are important macrocyclic compounds exhibiting a wide variety of applications in science and technology.[1,2,3,4,5,6,7,8,9,10,11,12,13] Their main characteristics are associated with the π-conjugated ring which imparts interesting physical and chemical properties, including the facility of stacking and yielding molecular films
As a matter of fact, tetrapyridyl porphyrins have already been modified with transition metal complexes in order to generate convenient building-blocks and connectors for assembling supramolecular systems and nanostructured materials.[18,19]
The coordination of ruthenium complexes to meso-pyridylporphyrins has provided rather versatile systems, in which the chemical and photochemical reactivity can be modulated by the electronic, structural and steric effects induced by the peripheral complexes.[27,28,29,30,31,32]
Summary
Phthalocyanines and porphyrins are important macrocyclic compounds exhibiting a wide variety of applications in science and technology.[1,2,3,4,5,6,7,8,9,10,11,12,13] Their main characteristics are associated with the π-conjugated ring which imparts interesting physical and chemical properties, including the facility of stacking and yielding molecular films. As a matter of fact, when the potential was changed from 0.50 to –0.20 V, a decrease in the intensity of the Soret and Q bands at 360 and 710 nm, and an increase of the absorbance at 550 nm were observed, corresponding to the formation of the porphyrazine radical anion species.
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