A simple synthetic approach to enhance the thermal luminescence sensitivity of Tb3+ complexes with thiacalix[4]arene derivatives through upper-rim bromination
| Autor: | Alexey N. Masliy, Asiya R. Mustafina, Dmitry V. Lapaev, Daina N. Buzyurova, Sergey N. Podyachev, Andrey M. Kuznetsov, Rinas N. Nagimov, Vasily M. Babaev, Svetlana N. Sudakova, Gulnaz Sh. Gimazetdinova, Victor V. Syakaev |
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| Rok vydání: | 2020 |
| Předmět: | |
| Zdroj: | Dalton Transactions. 49:8298-8313 |
| ISSN: | 1477-9234 1477-9226 |
| Popis: | The present work for the first time reports an application of the thiacalix[4]arene scaffold for the preparation of Tb3+ complexes possessing high thermal luminescence sensitivity in the physiological temperature range of 20–50 °C. Non-substituted thiacalix[4]arenes form luminescent complexes with Tb3+ ions, but they do not reveal any meaningful thermal sensitivity. To solve this problem, an upper-rim bromination of thiacalix[4]arenes, as well as distal bromination along with the embedding of two 1,3-diketone substituents are proposed as new simple synthetic approaches to enhance the thermal luminescence sensitivity of the Tb3+ complexes. A combination of mass spectrometry, NMR, UV-Vis and luminescence spectroscopy with quantum chemical calculations reveals a dimeric structure of the complexes formed by thiacalix[4]arenes with Tb3+ ions in DMF solutions. The steady-state luminescence of the Tb3+ complexes has demonstrated more than one order higher thermal sensitivity for the complexes of bromo-substituted ligands in comparison with the non-substituted thiacalix[4]arenes. The reasons for such behavior are discussed. The results highlight new opportunities for the thiacalix[4]arene platform for controlling ligand-to-metal energy transfer in terbium complexes and tuning their thermo-responsive luminescence properties. |
| Databáze: | OpenAIRE |
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