Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref>
Sergey N. Podyachev,
Svetlana N. Sudakova,
Rustem R. Zairov,
Victor V. Syakaev,
Alexey N. Masliy,
Michal Dusek,
Aidar T. Gubaidullin,
Alexey P. Dovzhenko,
Daina N. Buzyurova,
Dmitry V. Lapaev,
Gulnaz Sh. Mambetova,
Vasily M. Babaev,
Andrey M. Kuznetsov,
Asiya R. Mustafina
Affiliations
Sergey N. Podyachev
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Svetlana N. Sudakova
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Rustem R. Zairov
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Victor V. Syakaev
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Alexey N. Masliy
Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Str. 68, 420015 Kazan, Russia
Michal Dusek
Institute of Physics of the Czech Academy of Sciences, Na Slovance 2, 182 21 Prague, Czech Republic
Aidar T. Gubaidullin
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Alexey P. Dovzhenko
Department of Physical Chemistry, Kazan (Volga Region) Federal University, Kremlyovskaya Str. 18, 420008 Kazan, Russia
Daina N. Buzyurova
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Dmitry V. Lapaev
Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Sibirsky Tract 10/7, 420029 Kazan, Russia
Gulnaz Sh. Mambetova
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Vasily M. Babaev
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
Andrey M. Kuznetsov
Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Str. 68, 420015 Kazan, Russia
Asiya R. Mustafina
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia
The present work introduces the series of thiacalix[4]arenes (H4L) bearing different upper-rim substituents (R = H, Br, NO2) for rational design of ligands providing an antenna-effect on the NIR Yb3+-centered luminescence of their Yb3+ complexes. The unusual inclusive self-assembly of H3L− (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb3+:2HL3−] leads to efficient sensitizing of the Yb3+ luminescence for H4L (Br, NO2), while poor sensitizing is observed for ligand H4L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl3 and H4L(NO2) has revealed the transformation of the dimeric complexes into [4Yb3+:2L4−] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H4L(R = NO2), where the triplet level at 567 nm (17,637 cm−1) arisen from ILCT provides efficient sensitizing of the Yb3+ luminescence.
