3-Halochromones Through Oxidative α-Halogenation of Enaminones and its Photophysical Investigation: Another Case of Photo-induced Partially Aromatised Intramolecular Charge Transfer?

A versatile synthesis strategy for fluorescent 3-halo-4H-chromen-4-one derivatives is reported. The method involves the oxidative α-halogenation of enaminones performed by an efficient and sustainable oxidation system. The use of Oxone® in combination with KCl, KBr, or KI enables the preparation of 3-chloro-, 3-bromo-, or 3-iodo-4H-chromen-4-one in good to excellent yields, with great functional group tolerance where the protocol is amenable to gram-scale synthesis.

Organosulfur and Organoselenium Functionalized Benzimidazo[1,2-a]quinolines: From Experimental and Theoretical Photophysics to All-Solution-Processed OLEDs.

In this study, we present the synthesis of benzimidazo[1,2-a] quinoline-based heterocycles bearing organosulfur and organoselenium moieties through transition-metal-free cascade reactions involving a sequential intermolecular aromatic nucleophilic substitution (SN). Both sulfur and selenium derivatives presented absorption maxima located around 355 nm related to spin and symmetry allowing electronic π-π* transitions, and fluorescence emission at the violet-blue region (~440 nm) with relatively large Stokes shift. The fluorescence quantum yields were slightly influenced by the chalcogen, with the sulfur derivatives presenting higher values than the selenium analogs.

Evidence of a Photoinduced Electron-Transfer Mechanism in the Fluorescence Self-quenching of 2,5-Substituted Selenophenes Prepared through In Situ Reduction of Elemental Selenium in Superbasic Media.

A series of new 2,5-disubstituted selenophene derivatives are described from elemental selenium and 1,3-diynes in superbasic media. The activation of elemental selenium in a KOH/DMSO system allows cyclization with conjugated diynes at room temperature. The cyclization reaction is extended to a broad range of functional groups, for which photophysics were experimentally and theoretically investigated.

Light-Mediated Seleno-Functionalization of Organic Molecules: Recent Advances.

Organoselenium compounds constitute an important class of substances with applications in the biological, medicinal and material sciences as well as in modern organic synthesis, attracting considerable attention from the scientific community. Therefore, the construction of the C-Se bond via facile, efficient and sustainable strategies to access complex scaffolds from simple substrates are an appealing and hot topic. Visible light can be regarded as an alternative source of energy and is associated with environmentally-friendly processes.

Ultrasound-promoted regioselective synthesis of chalcogeno-indolizines by a stepwise 1,3-dipolar cycloaddition.

A series of new organochalcogen derivatives of indolizines was synthesized in moderate to excellent yields from pyridinium salts and chalcogeno-alkynes. The reaction can be carried out under thermal conditions or by sonochemical processes in short reaction times. The stepwise cycloaddition reaction forming chalcogeno-indolizines is regioselective and extends to a broad range of functional groups.

Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst.

In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.

Iron Oxide Nanoparticles Labeled with an Excited-State Intramolecular Proton Transfer Dye.

Excited-state intramolecular proton transfer (ESIPT) is a particularly well known reaction that has been very little studied in magnetic environments. In this work, we report on the photophysical behavior of a known ESIPT dye of the benzothiazole class, when in solution with uncoated superparamagnetic iron oxide nanoparticles, and when grafted to silica-coated iron oxide nanoparticles. Uncoated iron oxide nanoparticles promoted the fluorescence quenching of the ESIPT dye, resulting from collisions during the lifetime of the excited state.