Two Approaches for the Synthesis of Fused Dihydropyridines via a 1,6-Electrocyclic Reaction: Fluorescent Properties and Prospects for Application.

Reactions of penta-2,4-dienethioamides with acetylenedicarboxylic acid, methyl and ethyl esters, and methyl propiolate were systematically studied, and a number of new 2,3-dihydro-5H-thiazolo[3,2-a]pyridines (DTPs) and 4H,6H-pyrido[2,1-b][1,3]thiazines (PTZs) were prepared. A possible mechanism for a multistep domino transformation is suggested, and the key step is the 1,6-electrocyclic reaction. An additional alternative method for the synthesis of new heterocyclic systems was achieved. Evidence of the electrocyclic mechanism of a key step was collected from the analysis of the spatial structure of the synthesized bicyclic nonaromatic pyridines by X-ray diffraction and quantum chemical calculations, as well as from the thermodynamic quantities. DTPs exhibited yellow fluorescence in solution and yellow to red emissions in the solid state. Biological investigations demonstrated the ability of DTPs to penetrate living and fixed cells and presumably accumulate in lysosomes.

An effective and facile synthesis of new blue fluorophores on the basis of an 8-azapurine core.

A convenient synthesis of 2-aryl-2,4-dihydro-5H-[1,2,3]triazolo[4,5-d]pyrimidin-5-ones (DTPs) from 3,3-diamino-2-(arylazo)acrylonitriles through a versatile and readily accessible two-step procedure is described. Density functional theory (DFT) calculations were performed to explain the selectivity of the heterocyclization step, which predominantly afforded 6-amino-5-(arylazo)pyrimidin-2(1H)-thiones in chloroform or ethanol, and 2,3-dihydro-1,2,4-triazines in toluene or DMF. Novel 2-aryl-2,4-dihydro-5H-[1,2,3]triazolo[4,5-d]pyrimidin-5-ones were obtained in good yields and showed absorption in the ultraviolet region and good emission in the blue region. The photophysical properties of DTPs were better than those cited in select literature examples of 8-azapurines. Owing to the facile synthesis and good photophysical characteristics in an aqueous medium, the new DTPs should have potential applications as organic fluorophores in fluorescence imaging and materials science.

Fluorescent boron complexes based on new N,O-chelates as promising candidates for flow cytometry.

This study presents the synthesis and optical properties of a new class of bright green-yellow fluorescent dyes with potential applications in bioimaging. A facile synthetic route via the chelation of aryl(hetaryl)aminoacryloylthiophene scaffolds with a BF2 fragment is presented. The photophysical properties of the dyes are attributed to the nature and position of electron-donating and electron-withdrawing substituents. Upon coordination to a BF2 fragment, characteristic emission was observed, with λem ranging from 503 to 543 nm and quantum yields of 0.14-0.42. Compared with parent aryl(hetaryl)aminoacryloylthiophenes, a significant red shift in absorption (up to 480 nm in solution) and emission (up to 543 nm in solution and 610 nm in the solid state) and high chemical stability and photostability were observed. The electron-accepting character of the substituents on the terminal aromatic ring or replacing this fragment with pyridine or pyrazine moieties resulted in increased quantum yields. To gain insight into the electronic structures and optical properties, quantum mechanical calculations were performed. The results of (TD-)DFT calculations supported the structural and spectroscopic data and showed the features of electronic distribution in the frontier molecular orbitals and active electrophilic and nucleophilic sites in the compounds investigated. Synthesized BF2 complexes are promising dyes for cell imaging and flow cytometry owing to their ready penetration and accumulation in cells.

Highlights on the Road towards Highly Emitting Solid-State Luminophores: Two Classes of Thiazole-Based Organoboron Fluorophores with the AIEE/AIE Effect.

Developing a novel, small-sized molecular building block that may be capable of emitting light in the solid state is a challenging task and has rarely been reported in the literature. BF2 -containing dyes seem to be promising candidates towards this aim. Two series of new N^NBF2 complexes showing aggregation-induced emission (AIE) and aggregation-induced emission enhancement (AIEE) were designed and synthesized by means of a new protocol, which improved on the traditional method by employing microwave irradiation. The optical and photophysical properties of the BF2 complexes were investigated in depth. The synthesized complexes showed fluorescence in both solution and the solid state and, in a mixture of tetrahydrofuran/water, may aggregate into fluorescent nanoparticles. The experimental investigation was supported by quantum mechanical calculations. Their availability, stability, large Stokes shifts, and aggregation capabilities, along with their solid-state emission capability, render this new class of BF2 complexes promising AIEE/AIE fluorophores for further applications in the fields of fluorescence imaging and materials science.