Perylene Diimide Based Imine Cages for Inclusion of Aromatic Guest Molecules and Visible‐Light Photocatalysis

Abstract

A strategy for the development of visible-light-sensitive organic cage structures is reported. Enantiomeric imine cages with optical and electrochemical properties are developed employing perylene diimide (PDI) and tetraphenylethene subunits using dynamic covalent imine chemistry. Polycyclic aromatic hydrocarbons are encapsulated efficiently in the imine cage, and the guests interact with PDI units via supramolecular π-π interactions. Visible-light-driven Smiles rearrangement of 2aryloxybenzoic acids to aryl salicylates is achieved with high efficiency in the presence of the imine cage as the catalyst.

Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature

“…However, the two issues make the transformation more challenging. First, although some intramolecular electrophilic attack reactions of aryl carboxylic acid radicals to arenes have been reported [42][43][44][45][46][47] , the intermolecular electrophilic attack reaction of aryl carboxylic acid radicals to arenes has not been successfully explored. The intermolecular electrophilic attack of aryl carboxylic acid radicals to a blue LEDs, rt…”

“…Second, similarly to the intramolecular reaction, the formation of the more stable ester C-O bond should be the driving force of the diaryl ether C-O cleavage, as the C-O bond energies of an aryl ether and an ester are about 78.8 and 87-93 kcal/mol, respectively 49,50 . However, the possible intermediate B may lack a stronger driving force of C-O bond cleavage, compared with the six-membered ring intermediates in the intramolecular reactions [42][43][44][45][46][47] . As mentioned below, less than 10% yields of the product were obtained with the remaining starting material under the optimized reaction conditions for intramolecular reactions (Table 1, entries 1, 2).…”

Visible-Light Photoredox-Catalyzed C–O Bond Cleavage of Diaryl Ethers by Acridinium Photocatalysts at Room Temperature

“…S34). These reduction potentials indicate the prior formation of PC -• and the carboxylic acid radical [55][56][57][58][59][60] by a SET between PC* and the carboxylic acid anion. Furthermore, a quantum yield value of φ=0.20 was determined.…”

“…However, the two issues make the transformation more challenging. First, although some intramolecular electrophilic attack of aryl carboxylic acid radicals to arenes has been reported, [55][56][57][58][59][60] the intermolecular electrophilic attack of aryl carboxylic acid radicals to arenes has not been successfully explored. The intermolecular electrophilic attack of aryl carboxylic acid radicals to arenes was proposed in thermal decomposition of substituted dibenzoyl peroxides in diphenyl ether, in which the corresponding aryl benzoates were obtained in less than 39% yields with low selectivity.…”

“…[62][63] However, the possible intermediate B is indicated to lack stronger driving force of C-O bond cleavage, compared with the sixmembered ring intermediate in the intramolecular reaction. [55][56][57][58][59][60] As mentioned below, less than 10% product with the remained starting material was obtained under the optimized reaction conditions for intramolecular reactions (Table 1, entries 1, 2). Perhaps a Lewis acid could activate the ether.…”