Photocatalytic Carboxylation of Phenyl Halides with CO₂ by Metal‐Organic Frameworks Materials

Abstract

Main observation and conclusion In this work, important commercial pharmaceutical intermediates, phenylpropionic acid compounds, are successfully obtained by catalyzing the reaction of carbon dioxide with phenyl halides using MOF‐5, a typical metal‐organic framework (MOF) material. The influence of temperature, pressure, catalyst type and light on the reaction is investigated, and a 90.3% selectivity towards fluorophenylpropionic acid is reached. Significantly, the catalysts are effective for varied benzyl compounds containing different substituent groups. The catalysts are stable and remain active after three cycles.

Strong Host–Guest Dependence on the Emissive Properties of MOF-5 and [Zn2(BTTB)(DMF)2•(H2O)3]n

“…A closer look at why this is so, the main reason stems from a very small value of ε, which renders the J overlap integrals of the Forster and Dexter theories small, not to say negligible. This outcome (i.e., no or very low number of exciton hopping across the networks) indicates that the rich photocatalytic activity mentioned above ,,− ,,− ,− is not aided by the excitation energy migration. Therefore, the interior of the particles or nanoparticles does not contribute by the so-called antenna effect to the photochemical transformations that may occur at the surface of these porous objects.…”

“…Despite the rich photocatalytic properties of MOF-5 , ,,− ,,− ,− it is quite surprising that no S 1 –S 1 annihilation occurs. This result indicates that there no noticeable excitation energy migration across both MOF-5 ’s and MOF-D ’s scaffolding.…”

“…Metal–organic frameworks (MOFs) are known to exhibit rich heterogeneous excited-state-driven catalytic activity, and the semiconducting and emissive MOF-5 (3D-[ Zn 4 O­( 1,4-BDC ) 3 ] n ) (BDC = 1,4 - benzodicarboxylate) has been found to make no exception over the past several years. Indeed, semiconductor@ MOF-5 composites have become notorious for various photocatalytic applications such as H 2 -production, − O 2 -evolution, degradation of toxic organics and pollutants, − bacterial inactivation, − Cr­(VI)-reduction, and organic reactions , and pesticides .…”

Modulation of Excitonic Confinement of TiO2 in Molten Salts for Overall CO2 Photoreduction†

“…[ 1‐3 ] Photocatalytic CO 2 reduction is closely related to the photoinduced carrier migration kinetics. [ 4‐7 ] However, before reaching surface, most electron‐hole pairs are firmly bound through Coulombic interactions as excitons or undergo strong radiative recombination. Bulk configuration usually determines excitonic effects.…”

Stable CdII-Based Metal–Organic Framework as a Multiresponsive Luminescent Sensor for Acetylacetone, Salicylaldehyde, and Benzaldehyde with High Sensitivity and Selectivity

“…Metal–organic frameworks (MOFs) are considered promising materials with a high specific surface area, tunable structure and porosity, and good luminescence properties. − The use of luminescent metal–organic framework (LMOF) materials as chemical sensors has received much attention in the field. − However, multiresponsive luminescent LMOF sensors targeting organic molecules are quite uncommon. In general, a series of host–guest interactions between the host backbone and organic molecules can be used to induce different changes in the luminescence effect of LMOF materials, achieving multiple responses to organic compounds. − Tailor-made LMOF probe structures can provide specific host–guest interactions for selective recognition of target molecules.…”