Di-π-ethane Rearrangement of Cyano Groups via Energy-Transfer Catalysis.

Molecular rearrangement occupies a pivotal position among fundamental transformations in synthetic chemistry. Radical translocation has emerged as a prevalent synthetic tool, efficiently facilitating the migration of diverse functional groups. In contrast, the development of di-π-methane rearrangement remains limited, particularly in terms of the translocation of cyano functional groups. This is primarily attributed to the energetically unfavorable three-membered-ring transition state. Herein, we introduce an unprecedented di-π-ethane rearrangement enabled by energy-transfer catalysis under visible light conditions. This innovative open-shell rearrangement boasts broad tolerance toward a range of functional groups, encompassing even complex drug and natural product derivatives. Overall, the reported di-π-ethane rearrangement represents a complementary strategy to the development of radical translocation enabled by energy-transfer catalysis.

Synthesis, post-functionalization, and photoluminescence of contorted diazaphosphepine-based polycyclic aromatic heterocycles.

Heteroatom-doped organic π-conjugated molecules (OCMs) have become one type of emerging optoelectronic material with intriguing functionalities. Phosphorus (P)-doped OCMs are a special member of heteroatom-doped OCMs where rich P-chemistry is able to fine-tune their optoelectronic properties. Herein, we report a new series of nonplanar diazaphosphepine-based polycyclic aromatic heterocycles (DPP-PAHs). Efficient and mild double P-N cyclization allowed one to readily incorporate two P-centers in DPP-PAHs. With nonplanar diazaphosphepine rings, DPP-PAHs exhibit contorted structures in single crystal structures. The functionalization of double P-centers by H2O2 and S8 gave DPP-PAHs with PO and PS centers, respectively. Compared with the parent small molecule, the DPP-PAHs exhibit high photoluminescence quantum yields. Our experimental and theoretical studies further revealed that both P-environments and conjugated backbones have impacts on the photophysical properties of the DPP-PAHs.

Facile synthesis of Nafion-supported Pt nanoparticles with ultra-low loading as a high-performance electrocatalyst for hydrogen evolution reaction.

x%Pt-Naf-CV (Pt-Nafion-Cyclic Voltammetry) catalysts with homogeneously distributed platinum nanoparticles and ultra-low Pt loading are successfully synthesized by using a facile potential cycling approach. The as-synthesized 0.8%Pt-Naf-CV catalyst exhibits an enhanced electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4 solution, which obtains a low overpotential of 34 mV at 10 mA cm-2. The linear sweep voltammetry (LSV) curve of 0.8%Pt-Naf-CV catalyst is almost consistent with that of commercial Pt/C. However, the 0.8%Pt-Naf-CV catalyst displays a more excellent stability and durability in comparison with commercial Pt/C. Besides, the Pt loading of Pt/C (Pt-10 wt%) is about 10 times that of 0.8%Pt-Naf-CV catalyst. The improved electrocatalytic performances are derived from the synergistic effects of Pt and Nafion. The Nafion plays a significant role as a dispersant, carrier and structure directing agent on the morphology and size of the Pt catalyst. This result contributes a promising method to enhance the catalytic activity and reduce the amount of Pt.