To obtain luminescent lanthanide complexes with a low energy LMCT state the 2-(2′-mercaptophenyl)benzothiazolates, Ln(SSN)3, and 2-(2′-mercaptophenyl)benzoxazolates, Ln2(OSN)6 (Ln = Gd, Yb), were synthesized by the reaction of amides Ln[N(SiMe3)2]3 with respective thiophenols. Ytterbium complexes were structurally characterized by X-ray diffraction analysis. Cyclic voltammetry revealed that the deprotonated mercaptophenyl ligands have significantly lower oxidation potentials than their phenoxy analogues and some β-diketones. The photophysical properties of Gd and Yb compounds were studied both in solution and in the solid state. The fluorescence spectra of the compounds in solution display the bands of the keto and enol forms of the ligands. No energy transfer from the organic part to Yb3+ has been detected in solutions of both Yb complexes, whereas in solids an intense metal-centered emission in the near infrared region was observed. The solid Gd compounds exhibited room temperature phosphorescence caused by unusually efficient intersystem crossing facilitated by the essentially reducing properties of OSN and SSN ligands. To explain the sensitization process occurring in solids Yb2(OSN)6 and Yb(SSN)3 a specific non-resonant energy transfer mechanism via a ligand to metal charge transfer state has been proposed. Based on the Yb derivatives, NIR-emitting OLEDs with 860 μW cm−2 maximal irradiance were obtained. Their Gd counterparts showed bright electrophosphorescence (up to 1350 cd m−2) in the devices containing doped emission layers.
1 January 2018 in European Journal of Medicinal Chemistry
New 8-quinolinolate (Q) complexes of yttrium (1) and ytterbium (2) were synthesized by the reactions of Cp3Y and Yb[N(SiMe3)2]3 with 3 equiv. of 8-hydroxyquinoline in a DME solution. Single crystal X-ray analysis revealed the trinuclear molecular structure of the compounds Ln3Q9. The LDI-TOFMS investigation displayed that under the laser impact the compounds split off Q− anions to give Ln3Q8+, Ln2Q5+ and LnQ3+ moieties. In the negative mode spectra the anions Q− and LnQ4− were observed. The DFT calculations showed the decreased stability of cationic Ln-quinolinolate as compared with their anionic counterparts. Complex 2 which is used as an emitter in a three-layer OLED displayed a metal-centered emission at 979 nm and an intensity of 50 μW cm−2 at 15.5 V.
A (series) range of potential dimorpholinoquinazoline-based inhibitors of the PI3K/Akt/mTOR cascade was synthesized. Several compounds exhibited cytotoxicity towards a panel of cancer cell lines in the low and sub-micromolar range. Compound 7c with the highest activity and moderate selectivity towards MCF7 cells which express the mutant type of PI3K was also tested for the ability to inhibit PI3K-(signaling pathway) downstream effectors and associated proteins. Compound 7c inhibited the phosphorylation of Akt, mTOR, and S6K at 125–250 nM. It also triggered PARP1 cleavage, ROS production, and cell death via several mechanisms. Inhibition of PI3Kα was observed at a concentration of 7b 50 µM and of 7c 500 µM and higher, that can indicate minority PI3Kα as a target among other kinases in the titled cascade for 7c. In vivo studies demonstrated an inhibition of tumor growth in the colorectal tumor model. According to the docking studies, the replacement of the triazine core in gedatolisib (8) by a quinazoline fragment, and incorporation of a (hetero)aromatic unit connected with the carbamide group via a flexible spacer, can result in more selective inhibition of the PI3Kα isoform.