Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior
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 multi...
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MDPI AG
2020-09-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/21/18/6916 |
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| author | Anton Muravev Tatiana Gerasimova Robert Fayzullin Olga Babaeva Ildar Rizvanov Ayrat Khamatgalimov Marsil Kadirov Sergey Katsyuba Igor Litvinov Shamil Latypov Svetlana Solovieva Igor Antipin |
| author_facet | Anton Muravev Tatiana Gerasimova Robert Fayzullin Olga Babaeva Ildar Rizvanov Ayrat Khamatgalimov Marsil Kadirov Sergey Katsyuba Igor Litvinov Shamil Latypov Svetlana Solovieva Igor Antipin |
| author_sort | Anton Muravev |
| collection | DOAJ |
| description | 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 <i>1,2-alternate</i> 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 <b>3</b>. Excellent thermal stability and monolayer formation of nitrothiacalixarenes suggest their potential as functional dyes. |
| first_indexed | 2024-03-10T16:10:53Z |
| format | Article |
| id | doaj.art-a18e7413af504acd8ba9f2bd69bfed93 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T16:10:53Z |
| publishDate | 2020-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-a18e7413af504acd8ba9f2bd69bfed932023-11-20T14:28:52ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672020-09-012118691610.3390/ijms21186916Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation BehaviorAnton Muravev0Tatiana Gerasimova1Robert Fayzullin2Olga Babaeva3Ildar Rizvanov4Ayrat Khamatgalimov5Marsil Kadirov6Sergey Katsyuba7Igor Litvinov8Shamil Latypov9Svetlana Solovieva10Igor Antipin11Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, RussiaButlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008 Kazan, RussiaAchieving 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 <i>1,2-alternate</i> 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 <b>3</b>. Excellent thermal stability and monolayer formation of nitrothiacalixarenes suggest their potential as functional dyes.https://www.mdpi.com/1422-0067/21/18/6916nitrothiacalix[4]arenesMitsunobu alkylation<i>1,2-alternate</i> stereoisomerTG/DSC analysisX-ray diffractometryDFT study |
| spellingShingle | Anton Muravev Tatiana Gerasimova Robert Fayzullin Olga Babaeva Ildar Rizvanov Ayrat Khamatgalimov Marsil Kadirov Sergey Katsyuba Igor Litvinov Shamil Latypov Svetlana Solovieva Igor Antipin Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior International Journal of Molecular Sciences nitrothiacalix[4]arenes Mitsunobu alkylation <i>1,2-alternate</i> stereoisomer TG/DSC analysis X-ray diffractometry DFT study |
| title | Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior |
| title_full | Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior |
| title_fullStr | Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior |
| title_full_unstemmed | Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior |
| title_short | Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior |
| title_sort | thermally stable nitrothiacalixarene chromophores conformational study and aggregation behavior |
| topic | nitrothiacalix[4]arenes Mitsunobu alkylation <i>1,2-alternate</i> stereoisomer TG/DSC analysis X-ray diffractometry DFT study |
| url | https://www.mdpi.com/1422-0067/21/18/6916 |
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