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    Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior

    Year: 2020

    Journal: Int. J. Mol. Sci., Volume 21, SEP

    Authors: Muravev, A; Gerasimova, T; Fayzullin, R; Babaeva, O; Rizvanov, I; Khamatgalimov, A; Kadirov, M; Katsyuba, S; Litvinov, I; Latypov, S; Solovieva, S; Antipin, I

    Organizations: Russian Foundation for Basic ResearchRussian Foundation for Basic Research (RFBR) [20-33-70204]

    Keywords: nitrothiacalix[4]arenes; Mitsunobu alkylation; 1; 2-alternate stereoisomer; TG; DSC analysis; X-ray diffractometry; DFT study; Langmuir monolayers; reflection-absorption spectroscopy

    Achieving high thermal stability and control of supramolecular organization of functional dyes in sensors and nonlinear optics remains a demanding task. This study was aimed at the evaluation of thermal behavior and Langmuir monolayer characteristics of topologically varied nitrothiacalixarene multichromophores and phenol monomers. A nitration/azo coupling alkylation synthetic route towards partially O-substituted nitrothiacalixarenes and 4-nitrophenylazo-thiacalixarenes was proposed and realized. Nuclear magnetic resonance (NMR) spectroscopy and X-ray diffractometry of disubstituted nitrothiacalix[4]arene revealed a rare 1,2-alternate conformation. A synchronous thermal analysis indicated higher decomposition temperatures of nitrothiacalixarene macrocycles as compared with monomers. Through surface pressure/potential-molecular area measurements, nitrothiacalixarenes were shown to form Langmuir monolayers at the air-water interface and, through atomic force microscopy (AFM) technique, Langmuir-Blodgett (LB) films on solid substrates. Reflection-absorption spectroscopy of monolayers and electronic absorption spectroscopy of LB films of nitrothiacalixarenes recorded a red-shifted band (290 nm) with a transition from chloroform, indicative of solvatochromism. Additionally, shoulder band at 360 nm was attributed to aggregation and supported by gas-phase density functional theory (DFT) calculations and dynamic light scattering (DLS) analysis in chloroform-methanol solvent in the case of monoalkylated calixarene 3. Excellent thermal stability and monolayer formation of nitrothiacalixarenes suggest their potential as functional dyes.
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