Exploring Coumarin-Based Boron Emissive Complexes as Temperature Thermometers in Polymer-Supported Materials.

Three coumarin-based boron complexes (L1, L2 and L3) were designed and successfully incorporated into polymeric matrixes for evaluation as temperature probes. The photophysical properties of the complexes were carried out in different solvents and in the solid state. In solution, compound L1 exhibited the highest fluorescence quantum yield, 33%, with a positive solvatochromism also being observed on the absorption and emission when the polarity of the solvent increased. Additionally in the presence of anions, L1 showed a colour change from yellow to pink, followed by a quenching in the emission intensity, which is due to deprotonation with the formation of a quinone base. Absorption and fluorescence spectra of L1 were calculated at different temperatures by the DFT/B3LYP method. The decrease in fluorescence of compound L1 with an increase in temperature seems to be due to the presence of pronounced torsional vibrations of the donor and acceptor fragments relative to the single bond with C(carbonyl)-C (styrene fragment). L1, L2 and L3, through their incorporation into the polymeric matrixes, became highly emissive by aggregation. These dye@doped polymers were evaluated as temperature sensors, showing an excellent fluorescent response and reversibility after 15 cycles of heating and cooling.

Control of Fluorescence of Organic Dyes in the Solid-State by Supramolecular Interactions.

Fluorescent organic dyes play an essential role in the creation of new "smart" materials. Fragments and functional groups capable of free rotation around single bonds can significantly change the fluorescent organic dye's electronic structure under analyte effects, phase state transitions, or changes in temperature, pressure, and media polarity. Dependencies between steric and electronic structures become highly important in transition from a solution to a solid-state. Such transitions are accompanied by a significant increase in the dye molecular structure's rigidity due to supramolecular associates' formation such as H-bonding, π···π and dipole-dipole interactions. Among those supramolecular effects, H-bonding interactions, first of all, lead to significant molecular packing changes between loose or rigid structures, thus affecting the fluorescent dye's electronic states' energy and configuration, its fluorescent signal's position and intensity. All the functional groups and heteroatoms that are met in the organic dyes seem to be involved in the control of fluorescence via H-bonding: C-H···N, C-H···π, S = O···H-C, P = O···H, C-H···O, NH···N, C - H···C, C - H···Se, N-H···O, C - H···F, C-F···H. Effects of molecular packing of fluorescent organic dyes are successfully used in developing mechano-, piezo-, thermo- fluorochromes materials for their applications in the optical recording of information, sensors, security items, memory elements, organic light-emitting diodes (OLEDs) technologies.

Photolysis of 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins-Effective Fluorescence Decay.

Photophysical characteristics of new 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins have been measured. These coumarin derivatives are found to be effective fluorophores and show high values of quantum yields of fluorescence both in nonpolar and in polar solvents. The 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins turned to be photosensitive compounds and undergo photolysis under irradiation in the range of 310-465 nm. Photolysis is suggested to include retro-cyclization and retro-condensation steps. The process is accompanied by a sharp drop of fluorescence that can be of interest for the creation of new media in optical recording of information.

High-Energy and High-Power-Density Potassium Ion Batteries Using Dihydrophenazine-Based Polymer as Active Cathode Material.

Polymeric aromatic amines were shown to be very promising cathodes for lithium-ion batteries. Surprisingly, these materials are scarcely used for designing post-lithium batteries. In this Letter, we investigate the application of the high-voltage poly(N-phenyl-5,10-dihydrophenazine) (p-DPPZ) cathodes for K-ion batteries. The designed batteries demonstrate an impressive specific capacity of 162 mAh g-1 at the current density of 200 mA g-1, operate efficiently at high current densities of 2-10 A g-1, enabling charge and discharge within ∼1-4 min, and deliver the specific capacity of 125-145 mAh g-1 with a retention of 96 and 79% after 100 and 1000 charge-discharge cycles, respectively. Finally, these K-ion batteries with polymeric p-DPPZ cathodes showed rather outstanding specific power of >3 × 104 W kg-1, thus paving a way to the design of ultrafast and durable high-capacity metal-ion batteries matching the increasing demand for high power and high energy density electrochemical energy storage devices.