Modulating Charge Transfer Pathways to Enhance Photocatalytic Performance of the Metal-Organic Layer Nanosheet.

Two-dimensional metal-organic layer (MOL) nanosheets, as nonhomogeneous catalysts, show better optical activity in the field of photocatalysis due to their unique structural advantages. Current research focuses on how to modify the structure of 2D nanosheets by means of crystal engineering to modulate the intralayer electron transfer pathway and systematically investigate the impacts of size effect and electron transfer pathway on the energy utilization efficiency of crystalline materials. In the present work, a triple lophine-derived ligand was designed and prepared, which exhibits a large π-conjugation system and multiple D-A (D: donor, A: acceptor) electron transfer pathways. 2D MOL constructed with Cd ions can be exfoliated by physical sonication to obtain double-walled 2D MOL nanosheets. Compared with the bulk crystalline material, the 2D nanosheets exhibit better photovoltaic properties. Benefiting from the excellent structural advantages, 2D MOL nanosheets could be used as photocatalysts for a variety of aerobic oxidation reactions under mild conditions (10 W white LED, room temperature), such as the trifluoromethylation of coumarins, the synthesis of benzimidazole derivatives from aromatic diamines and aromatic aldehydes, and the preparation of 2,4,6-triarylpyridine derivatives, all with high conversion rates and selectivity (yield typically greater than 88%). The related results illustrate that the introduction of the photoactive triple-lophine unit into 2D MOL nanosheets can effectively modulate the electron transport mode and enhance energy utilization, which provides a new research idea for the development of nonhomogeneous photocatalysts aimed at the applications of visible light-driven organic conversion.

Tunable White Light Emission of a Metal-Organic Framework Based on a Bisquinoxaline Derivative by Introducing Red-Green Cationic Dyes.

The unique structural advantages give metal-organic frameworks (MOFs) a special use as host substrates to encapsulate organic dyes, which would result in specific host-guest composites for white-light phosphors. In this work, an anionic MOF exhibiting blue emission was constructed using bisquinoxaline derivatives as photoactive centers, which could effectively encapsulate rhodamine B (Rh B) and acriflavine (AF) to form an In-MOF ⊃ Rh B/AF composite. By simply adjusting the amount of Rh B and AF, the emitting color of the resulting composite could be easily adjusted. The formed In-MOF ⊃ Rh B/AF composite exhibits broadband white light emission with ideal Commission International ed'Eclairage (CIE) coordinates of (0.34, 0.35), a color rendering index of 80.8, and a moderately correlated color temperature value of 5193.96 K. This strategy can be easily extended to other blue-emitting MOFs and dyes, thus opening up new prospects for the development of white-light-emitting materials.

Catalyst-Free Three-Component Tandem CDC Cyclization: Convenient Access to Isoindolinones from Aromatic Acid, Amides, and DMSO by a Pummerer-Type Rearrangement.

A catalyst-free multicomponent CDC reaction is rarely reported, especially for the intermolecular tandem CDC cyclization, which represents an important strategy for constructing cyclic compounds. Herein, a three-component tandem CDC cyclization by a Pummerer-type rearrangement to afford biologically relevant isoindolinones from aromatic acids, amides, and DMSO, is described. This intermolecular tandem reaction undergoes a C(sp(2) )-H/C(sp(3) )-H cross-dehydrogenative coupling, C-N bond formation, and intramolecular amidation. A notable feature of this novel protocol is avoiding a catalyst and additive (apart from oxidant).