Transformation of PMMA from sunlight-blocking to sunlight-activated coupled with DNH photocatalytic platform for oxidative coupling of amines and generation/regeneration of LDC/NADH.

The photocatalytic oxidation and generation/regeneration of amines to imines and leucodopaminechrome (LDC)/NADH are subjects of intense interest in contemporary research. Imines serve as crucial intermediates for the synthesis of solar fuels, fine chemicals, agricultural chemicals, and pharmaceuticals. While significant progress has been made in developing efficient processes for the oxidation and generation/regeneration of secondary amines, the oxidation of primary amines has received comparatively less attention until recently. This discrepancy can be attributed to the high reactivity of imines generated from primary amines, which are prone to dehydrogenation into nitriles. In this study, we present the synthesis and characterization of a novel polymer-based photocatalyst, denoted as PMMA-DNH, designed for solar light-harvesting applications. PMMA-DNH incorporates the light-harvesting molecule dinitrophenyl hydrazine (DNH) at varying concentrations (5%, 10%, 20%, 30%, and 40%). Leveraging its high molar extinction coefficient and slow charge recombination, the 30% DNH-incorporated PMMA photocatalyst proves to be particularly efficient. This photocatalytic system demonstrates exceptional yields (96.5%) in imine production and high generation/regeneration rates for LDC/NADH (65.27%/78.77%). The research presented herein emphasizes the development and application of a newly engineered polymer-based photocatalyst, which holds significant promise for direct solar-assisted chemical synthesis in diverse commercial applications.

Selective aerobic coupling of amines to imines using solar spectrum-responsive flower-like Nen-graphene quantum dots (GQDs) decorated with 2, 4-dinitrophenylhydrazine (PH) as a photocatalyst.

Indeed, the development of ecologically benign molecular fabrication methods for highly efficient graphene quantum dots-based photocatalysts is of great significant. Graphene quantum dots-based photocatalysts have promising applications in various field, including environmental remediation, energy conversion, and splitting of water. However, ensuring resource reusability and minimizing the environmental impact are crucial considerations in the development. From this perspective, attention has also been paid to the creation of easy to make solar light harvesting graphene quantum dots-based photocatalysts for synthesising pharmaceuticals and functional imines compounds. Imines are excellent significant building blocks in pharmaceutical chemistry and excellent examples of these valuable compounds' synthetic intermediates, and the environmentally friendly oxidative synthesis of imines from amines. Therefore, herein, we designed a facile and efficient condensation route to synthesize the Nen-GQDs@PH photocatalyst. This route involves coupling of 2,4-dinitrophenylhydrazine (PH) with nitrogen-enriched graphene quantum dots (Nen-GQDs). The Nen-GQDs@PH as photocatalyst functions in a highly selective and efficient manner, leading to high amines conversion efficiency to imines (95%). Our results highlight a novel and environmentally safe approach for generating highly selective imines from various types of amines, setting a new benchmark in the current research field.

In Situ Prepared Solar Light-Driven Flexible Actuated Carbon Cloth-Based Nanorod Photocatalyst for Selective Radical-Radical Coupling to Vinyl Sulfides.

A global challenge faced by light harvesting photocatalyst is how to promote the selective organic transformation, such as C-S bond formation via radical-radical coupling under solar light. Here, we report a two-dimensional covalent organic frameworks (2D-COFs), poly (perylene-imide-benzoquinone) nanorod through in situ condensation on flexible activated carbon cloth (PPIBNR-FACC) to function as a light harvester material for highly selective radical-radical coupling to vinyl sulfides (i.e. C-S bond activation). Such a structure supports charge transfer from PPIBNR to FACC, which is essential for the selective radical-radical coupling. Hence, organic transformation is attaining high yields and selectivity (˜99%) under solar light using in situ prepared PPIBNR-FACC photocatalyst. The structural virtues of PPIBNR-FACC will trigger the utmost investigations into designable and versatile 2D-COFs for fine chemical synthesis.