Conjugated 1,3-diketone calix[4]arenes: synthesis, complexation and structure-dependent sensitizing of Eu3+-luminescence

Conjugated 1,3-diketone calix[4]arenes: synthesis, complexation and structure-dependent sensitizing of Eu3+-luminescence Научная публикация

Журнал

Polyhedron
ISSN: 1873-3719 , E-ISSN: 0277-5387

Вых. Данные

Год: 2024, Том: 264, Номер статьи : 117271, Страниц : DOI: 10.1016/j.poly.2024.117271

Авторы

Podyachev Sergey N. ¹ , Sudakova Svetlana N. ¹ , Shvedova Anastasiya E. ¹ , Deltsov Ilya D. ² , Masliy Alexey N. ³ , Sh. Mambetova Gulnaz ¹ , Syakaev Victor V. ¹ , Vatsouro Ivan M. ⁴ , Gorbunov Alexander N. ⁴ , Bezzubov Stanislav I. ⁵ , Lapaev Dmitry V. ⁶ , Kuznetsov Andrey M. ³ , Kovalev Vladimir V. ⁴ , Mustafina Asiya R. ¹

Организации

1	Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russian
3	Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Str. 68, 420015, Kazan, Russia
4	Department of Chemistry, M. V. Lomonosov Moscow State University, Lenin’s Hills 1, 119991 Moscow, Russia
5	Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, 119991 Moscow, Russia
6	Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Sibirsky Tract 10/7, 420029 Kazan, Russia

This work presents new type of bis-1,3-diketone calix[4]arene derivatives, in which the chelate groups are directly conjugated through the carbonyl carbon atom with aromatic fragments of calix[4]arene, and their lower rims bear four propoxy groups or pairs of hydroxy and propoxy groups. Tetrapropoxy-calix[4]arene is synthesized by acylation of magnesium enolates of a calix[4]arene ketone with 1-benzoylbenzotriazoles, and the dipropoxy analogue is obtained by bromination of bis(chalcone)-calix[4]arene, followed by methanolysis and hydrolysis. Significant conjugation of 1,3-diketo groups with the π-system of calix[4]arene is revealed for calixarenes of both types. Analysis of complexes formed by the ligands using the UV–Vis and NMR diffusion methods in combination with DFT calculations makes it possible to identify differences in the modes of complex formation of di- and tetrapropoxy- substituted ligands. It is demonstrated that a more enhanced sensibilization of Eu3+-luminescence in complexes with dipropoxy-calix[4]arene compared to that for complexes with tetrapropoxy-counterpart correlates with the formation of a tetrameric structure, in which the binding of Eu3+ ions does not disturb the conjugation of 1,3-diketonate moieties with aromatic calix[4]arene fragments. This is quite different from the significant disturbance of conjugation during intramolecular bis-chelation of Eu3+ ion by 1,3-diketo groups of tetraalkyl substituted ligand.

Podyachev S.N. , Sudakova S.N. , Shvedova A.E. , Deltsov I.D. , Masliy A.N. , Sh. Mambetova G. , Syakaev V.V. , Vatsouro I.M. , Gorbunov A.N. , Bezzubov S.I. , Lapaev D.V. , Kuznetsov A.M. , Kovalev V.V. , Mustafina A.R.
Conjugated 1,3-diketone calix[4]arenes: synthesis, complexation and structure-dependent sensitizing of Eu3+-luminescence
Polyhedron. 2024. V.264. 117271 . DOI: 10.1016/j.poly.2024.117271 WOS Scopus OpenAlex

Web of science:	WOS:001348954000001
Scopus:	2-s2.0-85207692366
OpenAlex:	W4403681074

БД	Цитирований
Scopus	3
Web of science	2
OpenAlex	3