Creating the Ideal Push‐Pull System for Electrocatalysis: A Comparative Study on Symmetrical and Asymmetrical Cardanol‐based Cobalt Phthalocyanines

Abstract

A symmetrical cardanol‐based cobalt phthalocyanine (Pc) along with its asymmetrical acid‐based derivatives were synthesized and applied in the electrocatalysis of hydrazine. Despite the inhibition of electron movement by the bulky cardanol‐based substituent throughout the series of molecules, an ideal combination of substituents was established in GCE‐3 (2,9,16‐tris(3‐pentadecylphenoxy)‐23‐mono propionic acid phthalocyanato cobalt (II)) where a limit of detection (LoD) value of 5.10 μM (signal to noise ratio=5) was recorded for the detection of hydrazine. The results obtained serve as an illustration that the combination of electron‐donating and electron‐withdrawing substituents has a significant influence on the complete functioning of the phthalocyanine molecule(s) being investigated.

A versatile, divergent route for the synthesis of ABAC tetraazaporphyrins: molecularly engineered, push–pull phthalocyanine-type dyes

“…9b,35 As a proof of concept, the controlled synthesis of a pushpull, ABAC dibenzoporphyrazine, containing a linear arrangement of the donor and acceptor fragments, has been prepared. This molecularly engineered phthalocyanine-type dye, which features the prototypical structure of a donor-p-bridge-acceptor, improves light-harvesting properties, and opens a route to push-pull phthalocyanine-like compounds of interest, for example, in DSSCs, 10a,21 electrocatalysis, 36 nonlinear optics, 37 or amphiphilic chromophores for biological applications. 38 We are currently applying the developed method to the preparation of regioisomerically pure compounds in related ABAC systems by examining the separation of regioisomers, in order to study their properties as photosensitizers in DSSCs.…”

Correlating theory with experimental data on the effect of symmetry on the electrocatalytic behaviour of Co phthalocyanines

“…In addition to the electrochemical studies performed, a DFT analyses is performed to better comprehend the reactivity of the complexes in response to hydrazine. The detection of hydrazine using CoPcs has been reported before however, the substituents involved have been derived from phenolic compounds which introduce the highly electronegative oxygen atom through the C-O-C bond [9,12,13]. In this work we use CoPcs where the dominant substituent is directly linked to the Pc ring (through a C-C bond).…”

Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells

“…The use of different motifs as the B unit allows modulation of the donor–acceptor character of the dye, as well as the distance and the orientation of the acid function with respect to the macrocycle, these characteristics being central in the performance of the dye [ 29 , 30 ]. Push–pull, donor-π-acceptor dyes, containing carboxylic and other polar functions, find applications as photosensitizers in different fields [ 31 , 32 , 33 , 34 , 35 , 36 , 37 ].…”