Preparation of Langmuir-Blodgett Films from Quinoxalines Exhibiting Aggregation-Induced Emission and Their Acidochromism.

The development of aggregation-induced emission (AIE)-exhibiting compounds heavily relies on our evolving comprehension of their behavior at interfaces, an understanding that still remains notably limited. In this study, we explored the preparation of two-dimensional (2D) sensing films from 2,3-diphenylquinoxaline-based diazapolyoxa- and polyazamacrocycles displaying AIE via the Langmuir-Blodgett (LB) technique. This systematic investigation highlights the key role of the heteroatom-containing tether of 2,3-diphenylquinoxalines in the successful fabrication of Langmuir layers at the air-water interface and the transfer of AIE-emitting supramolecular aggregates onto solid supports. Using both diazapolyoxa- and polyazamacrocycles, we prepared AIE-exhibiting monolayer films containing emissive supramolecular aggregates on silica, mica, and quartz glass and characterized them using ultraviolet-visible (UV-vis) and photoluminescence (PL) spectroscopies, atomic force microscopy (AFM) imaging, and fluorescence microscopy. We also obtained multilayer AIE-emitting films through the LB technique, albeit with increased complexity. Remarkably, by employing the smallest macrocycle N2C3Q, we successfully prepared LB films suitable for the visual detection of acidic vapors. This sensing material, which contains a much lesser amount of organic dye compared with traditional drop-cast films, can be regenerated and utilized for real-life sample analysis, such as monitoring the presence of ammonia in the air and the freshness of meat.

Quinoxaline-based azamacrocycles: synthesis, AIE behavior and acidochromism.

The development of luminescent molecular materials has advanced rapidly in recent decades, primarily driven by the synthesis of novel emissive compounds and a deeper understanding of excited-state mechanisms. Herein, we report a streamlined synthetic approach to light-emitting diazapolyoxa- and polyazamacrocycles N2CnOxQ and NyCnQ (n = 3-10; x = 2, 3; y = 2-5), incorporating a 2,3-diphenylquinoxaline residue (DPQ). This synthetic strategy based on macrocyclization through Pd-catalyzed amination reaction yields the target macrocycles in good or high yields (46-92%), enabling precise control over their structural parameters. A key role of the PhPF-tBu ligand belonging to the JosiPhos series in this macrocyclization was elucidated through DFT computation. This macrocyclization reaction eliminates the need for complex protecting-deprotecting procedures of secondary amine groups, offering a convenient and scalable method for the preparation of target compounds. Moreover, it boasts a potentially broad substrate scope, making it promising for structure-properties studies within photophysics, sensor development, and material synthesis. Photophysical properties of representative macrocycles were investigated, employing spectroscopic techniques and DFT computation. It was demonstrated that DPQ-containing macrocycles display aggregation-induced emission in a DCM-hexane solvent mixture despite the presence of flexible tethers within their structures. Single-crystal X-ray diffraction analysis of a representative compound N2C8O3Q allowed us to gain deeper insight into its molecular structure and AIE behaviour. The emissive aggregates of the N2C10O3Q macrocycle were immobilized on filter paper yielding AIE-exhibiting test strips for measuring acidity in vapors and in aqueous media.

Polyoxa- and Polyazamacrocycles Incorporating 6,7-Diaminoquinoxaline Moiety: Synthesis and Application as Tunable Optical pH-Indicators in Aqueous Solution.

Synthetic approach to fluorescent polyaza- and polyoxadiazamacrocycles comprising a structural fragment of 6,7-diamino-2,3-diphenylquinoxaline has been elaborated using Pd-catalyzed amination providing target compounds in yields up to 77%. A series of nine novel N- and N,O-containing macrocyclic ligands differing by the number of donor sites and cavity size has been obtained. These compounds possess well-pronounced fluorescent properties with emission maxima in a blue region in aprotic solvents and high quantum yields of fluorescence, while in proton media, fluorescence shifts towards the green region of the spectrum. Using macrocycles 5c and 5e as examples, we have shown that such compounds can serve as dual-channel (colorimetric and fluorimetric) pH indicators in water media, with pH transition point and response being dependent on the macrocycle structure due to different sequences of protonation steps.

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines.

N-heteroaryl substituted adamantane-containing amines are of substantial interest for their perspective antiviral and psychotherapeutic activities. Chlorine atom at alpha-position of N-heterocycles has been substituted by the amino group using convenient nucleophilic substitution reactions with a series of adamantylalkylamines. The prototropic equilibrium in these compounds was studied using NMR spectroscopy. The introduction of the second amino substituent in 4-amino-6-chloropyrimidine, 2-amino-chloropyrazine, and 1-amino-3-chloroisoquinoline was achieved using Pd(0) catalysis.