Catechol-Containing Schiff Bases on Thiacalixarene: Synthesis, Copper (II) Recognition, and Formation of Organic-Inorganic Copper-Based Materials.

Pavel Padnya,Artur Boldyrev,Maxim Arsenyev,Igor Shiabiev,Svetlana Baryshnikova,Olga Terenteva,Ivan Stoikov,Ksenia Shibaeva,Alexander Gerasimov,Denis Grishaev,Artur Khannanov,Yurii Shtyrlin

doi:10.3390/molecules26082334

Pavel Padnya, Artur Boldyrev + Show 10 more

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https://doi.org/10.3390/molecules26082334

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Abstract

For the first time, a series of catechol-containing Schiff bases, tetrasubstituted at the lower rim thiacalix[4]arene derivatives in three stereoisomeric forms, cone, partial cone, and 1,3-alternate, were synthesized. The structure of the obtained compounds was proved by modern physical methods, such as NMR, IR spectroscopy, and HRMS. Selective recognition (Kb difference by three orders of magnitude) of copper (II) cation in the series of d-metal cations (Cu2+, Ni2+, Co2+, Zn2+) was shown by UV-vis spectroscopy. Copper (II) ions are coordinated at the nitrogen atom of the imine group and the nearest oxygen atom of the catechol fragment in the thiacalixarene derivatives. High thermal stable organic-inorganic copper-based materials were obtained on the base of 1,3-alternate + Cu (II) complexes.

Highlights

The structure of the obtained compounds was proved using a number of modern physical methods, such as NMR, IR, UV-vis spectroscopy, and high-resolution mass spectrometry
The logarithms of binding constants were found to be similar for all three stereoisomers (cone + Cu (II): 5.04; partial cone + Cu (II): 5.36; 1,3-alternate + Cu (II): 5.46)
It was shown by a series of physical methods, that the copper (II) ions were coordinated at the nitrogen atom of the imine group and the nearest oxygen atom of the catechol fragment in thiacalixarene derivatives

Summary

Introduction

The design of new hybrid materials with unusual and unique properties is a promising challenge due to the development of modern industry and the possibilities of their use in advanced technologies [1,2,3,4,5,6,7]. Metals and their ions, such as silver, gold, and copper, are often applied in the composition of organic-inorganic materials, such as an inorganic component [8]. Such materials have high thermal and electrical conductivity, biological activity (for example, antifungal, antibacterial), and are used as catalysts and sensors [12,13,14,15]

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