Synthesis, Spectroscopic Properties and Redox Behavior Kinetics of Rare-Earth Bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato Metal Complexes with Er, Lu and Yb.

Dmitry A Erzunov,Tatiana V Tikhomirova,Natalia P Domareva,Anna A Botnar,Arthur S Vashurin

doi:10.3390/molecules26082181

Dmitry A Erzunov, Tatiana V Tikhomirova + Show 3 more

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https://doi.org/10.3390/molecules26082181

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Abstract

Novel bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato of complexes erbium, lutetium and ytterbium were synthesized using a template fusion method to prevent any polymerization process. The complexes were separated from the reaction mixtures and characterized by NMR, IR and electron absorption spectroscopy. The spectroscopic properties of the metal phthalocyaninates in chloroform, acetone and tetrahydrofuran were studied. The regular bathochromic shift in the Er–Yb–Lu series was determined. In acetone medium all the complexes obtained were found to exist in an equilibrium state between neutral and reduced forms. The linearity of Lambert-Bouger-Beer curves makes it possible to study the kinetics of redox processes in the presence of phenylhydrazine and bromine. The lutetium complex showed better reducing properties and turned fully into the reduced form, while the erbium and ytterbium ones changed only partially. Upon oxidizing all the phthalocyaninates transformed into a mixture of oxidized and neutral-radical forms. The extinction coefficients and effective redox constants were calculated.

Highlights

Phthalocyanines are widely used in many areas of activity, such as catalysis [1,2], light industry [3,4], medicine [5,6], linear and nonlinear optics and energy storage devices [7,8,9]
The scope of usage directly depends on the structure of the molecule, namely on the nature of peripheral and non-peripheral substituents, the presence or absence of a central metal atom
Unsubstituted phthalocyanine is practically insoluble in most organic media, which greatly limits the scope of its application

Summary

Introduction

Phthalocyanines are widely used in many areas of activity, such as catalysis [1,2], light industry [3,4], medicine [5,6], linear and nonlinear optics and energy storage devices [7,8,9] Such a widespread usage is associated with the high stability of these molecules, the presence of intense light absorption in the visible range, the flexibility of the design of structures [10,11,12], the possibility of introducing practically any metal atom into the central cavity [13,14,15] and the possession of significant coordination properties. Unsubstituted phthalocyanine is practically insoluble in most organic media, which greatly limits the scope of its application

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Discussion

Conclusion