Bodipy-Based Metal–Organic Frameworks Transformed in Solid States from 1D Chains to 2D Layer Structures as Efficient Visible Light Heterogeneous Photocatalysts for Forging C–B and C–C Bonds

Abstract

Boron dipyrromethene (also known as bodipy), as a class of versatile and robust fluorophores and a structural analogue of porphyrins, has received a great deal of interests in the field of light-harvesting and energy-transfer processes. However, the fabrication of bodipy monomers into metal−organic frameworks (MOFs) and the exploitation of their potential still lags behind the porphyrin MOFs. In this work, two bodipy-based MOFs, BMOF 1D with 1D chain structure and BMOF 2D with 2D layer structure, were assembled by using dicarboxyl-functionalized bodipy ligands. BMOF 1D can also be converted to BMOF 2D by inserting additional ligands into BMOF 1D to cross-link the adjacent chains into the rhombic grid layer. During this process, spontaneous exfoliation occurred simultaneously and resulted in the formation of several hundred nanometer thickness BMOF 2D (nBMOF 2D), which can be further exfoliated into onelayer MOF nanosheets (BMON 2D) by using the ultrasonic liquid exfoliation method in a high yield. Featuring the distinct bodipy scaffolds in the porous frameworks, both BMOF 2D and BMON 2D displayed high reactivity and recyclability in the photocatalytic inverse hydroboration and cross-dehydrogenative coupling reactions to afford α-amino organoborons and α-amino amides in moderate to high yields. This work not only highlights the cascade utilization of ligand installation and ultrasonic liquid exfoliation methods to provide the single-layer MOF sheets in high yields but also advances the bodipy-based MOFs as a new type of heterogeneous photocatalysts in the forging of C−B and C−C bonds driven by visible light.

Ligand-regulated photoinduced electron transfer within metal–organic frameworks for efficient photocatalysis

“…Yield: 89%. 1 H NMR (500 MHz, CDCl 3 ) δ 8.58 (d, J = 2.4 Hz, 2H), 7.80 (d, J = 4.7 Hz, 2H), 7.51 (dd, J = 9.1, 2.4 Hz, 2H), 7.17 (d, J = 1.9 Hz, 2H), 6.57 (d, J = 9.1 Hz, 2H). 13 O.…”

“…Yield: 72%. 1 biphenyl]-4-yl)-9-oxo-9,10-dihydroacridine-2,7-diyl)dibenzoate (5.00 g, 7.43 mmol) and NaOH (4.4 g, 0.11 mol) were dissolved in a mixture containing 50 mL ethanol and 50 mL H 2 O. The mixture was then refluxed for 24 hours.…”

“…Amines with phenyl groups were successfully converted into the desired products with moderate conversions to N-phenylic arylation products. Furthermore, functional group tolerance was examined by coupling nitrile compounds (1) with various amines (2) (Table 2). Satisfyingly, a broad variety of functional groups such as piperidines (3ab), morpholines (3ac) and acyclic amines (3ad and 3ae) provided desirable results.…”

“…Over the past few decades, MOFs have garnered significant attention for their immense potential in various photocatalytic transformations. [1][2][3] Incorporating organic dyes into MOFs provides high-density photoactive sites, enabling the dyes to be linked together and well isolated by metal ions. This strategy overcomes the challenges posed by non-recyclable catalysts and the strong aggregation and polymerization phenomena of organic dyes, which greatly limit the development and utilization of various homogeneous dye-based photocatalysts.…”

Design, Synthesis and Characterization of Palladium‐Functionalized Covalent Organic Framework and Its Application as Heterogeneous Catalysis for C−H Arylation of Azoles

“…Compared to homogeneous catalysts, heterogeneous ones are arguably more attractive in the chemical industry due to their easier separation and recycling. [23][24][25] Although a large number of carriers such as natural species, inorganic materials, clays, magnetic material, biochar, organic polymers and metal-organic frameworks, have been applied as the support for constructing heterogeneous catalysts, [26][27][28][29][30] the stability, recyclability, leaching, and economic, environmental issues need to be further improved.…”