Ultrasmall CsPbBr3 Nanocrystals as a Recyclable Heterogeneous Photocatalyst in 100% E- and Anti-Markovnikov Sulfinylsulfonation of Terminal Alkynes.

The precise synthesis of ultrasmall, monodisperse CsPbBr3 nanocrystals is crucial due to their enhanced photophysical properties resulting from strong quantum confinement effects. Traditional methods struggle with size control, complicating synthesis. Although CsPbBr3 nanocrystals find applications in LEDs and photovoltaics, their use in photocatalysis for organic reactions remains limited. Our study introduces ultrasmall TBIA-CsPbBr3 nanocrystals (∼5.6 nm), synthesized via a three-precursor hot injection method using tribromoisocyanuric acid (TBIA) as a bromine precursor for the first time. These nanocrystals exhibit a near-unity photoluminescence quantum yield (PLQY) of 0.99 and an elevated oxidation potential of +1.80 V. We demonstrate their efficacy as recyclable heterogeneous photocatalysts in a one-pot, 100% E-selective, anti-Markovnikov sulfinylsulfonation of terminal alkynes under visible light, achieving a high product conversion rate (PCR) of 62,500 µmol g-1 h-1 and recyclability for up to five cycles. Density functional theory (DFT) calculations support the exclusive formation of the E-isomer. TBIA-CsPbBr3 outperforms other CsPbBr3 perovskites in photocatalysis, with superior efficiency attributed to their extended excited-state lifetime and higher surface area, which accelerates the organic transformation process.

N-Halosuccinimide-CeCl3 Transient Charge-Transfer Complexes as Semi Heterogeneous Photocatalyst in Cyclization of N-Propargylamides.

In this work, we used photoinert anhydrous cerium(III) chloride, to form a transient charge-transfer (CT) complex with NXS (N-bromosuccinimide or NBS and N-iodosuccinimide or NIS) in acetonitrile. These transient CT complexes acted as a semi-heterogeneous photocatalyst. These complexes allowed the Ce(III) ions to absorb light, turning them into strong electron donors that transferred electrons to NXS. This created halide radicals from NXS radical anions, helping to turn N-propargylamides into oxazole aldehydes. Experiments with DMPO and spin-trapping showed that a radical-based mechanism followed a single electron transfer (SET) pathway. Notably, CeCl3 was reused after the reaction without much decomposition, as it was regenerated and separated through simple filtration.

Stereoselective Synthesis of Z-Styryl Sulfides from Nucleophilic Addition of Arylacetylenes and Benzyl Thiols.

The stereoselective synthesis of Z-anti-Markovnikov styryl sulfides via an anionic thiolate-alkyne addition reaction was achieved when the terminal alkynes and benzyl mercaptans were reacted using tBuOLi (0.5 equiv) in EtOH under ambient conditions. Exclusive stereoselectivity (ca. 100%) was achieved by stereoelectronic control via anti-periplanar and anti-Markovnikov addition of benzylthiolates to phenylacetylenes. Solvolysis of lithium thiolate ion pairs in ethanol significantly suppresses the competing formation of the E-isomer. A remarkable enhancement of the Z-selectivity under a longer reaction time was observed.

Activation of C-Br Bond of CBr4 and CBrCl3 Using 9-Mesityl-10-methylacridinium Perchlorate Photocatalyst.

Herein, we report the activation of the C-Br bond of CBrX3 (X = Cl, Br) using 9-mesityl-10-methylacridinium perchlorate as a visible-light (12W blue LED, 450-455 nm) photocatalyst for the synthesis of gem-dihaloenones from terminal alkynes. An electron transfer from CBrX3 to Mes-Acr-MeClO4 led to the formation of •+CBrX3 which subsequently resulted in the intermediate +CX3. Next, C-C cross-coupling of +CX3 with terminal alkynes was the key path to obtain the gem-dihaloenones. Radical trapping experiments with TEMPO, BHT, and Stern-Volmer quenching studies helped to understand that the reaction proceeded via the SET mechanism.