Podyachev Sergey N, Sudakova Svetlana N, Zairov Rustem R, Syakaev Victor V, Masliy Alexey N, Dusek Michal, Gubaidullin Aidar T, Dovzhenko Alexey P, Buzyurova Daina N, Lapaev Dmitry V, Mambetova Gulnaz Sh, Babaev Vasily M, Kuznetsov Andrey M, Mustafina Asiya R
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia .
Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Str. 68, 420015 Kazan, Russia.
Molecules. 2022 Oct 11;27(20):6793. doi: 10.3390/molecules27206793.
The present work introduces the series of thiacalix[4]arenes (HL) bearing different upper-rim substituents (R = H, Br, NO) for rational design of ligands providing an antenna-effect on the NIR Yb-centered luminescence of their Yb complexes. The unusual inclusive self-assembly of HL (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb:2HL] leads to efficient sensitizing of the Yb luminescence for HL (Br, NO), while poor sensitizing is observed for ligand HL (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl and HL(NO) has revealed the transformation of the dimeric complexes into [4Yb:2L] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of HL(R = NO), where the triplet level at 567 nm (17,637 cm) arisen from ILCT provides efficient sensitizing of the Yb luminescence.
本工作介绍了一系列在上缘带有不同取代基（R = H、Br、NO）的硫杂杯[4]芳烃（HL），用于合理设计配体，这些配体对其Yb配合物的近红外Yb中心发光具有天线效应。通过单晶XRD分析揭示了HL（Br）通过Brπ相互作用进行的不寻常的包结自组装。热力学上有利形成的二聚体配合物[2Yb:2HL]导致HL（Br，NO）对Yb发光的有效敏化，而对于配体HL（H）则观察到较差的敏化效果。对从YbCl和HL（NO）的碱化DMF溶液中分离出的单晶进行的X射线分析表明，二聚体配合物转变为具有立方烷状簇结构的[4Yb:2L]配合物。溶液中配合物的发光特性揭示了HL（R = NO）独特的天线效应，其中源于ILCT的567 nm（17,637 cm）处的三重态能级对Yb发光提供了有效的敏化。
