Terarylenes as Photoactivatable Hydride Donors

Abstract

Terarylene frameworks containing benzothiazole as a photoprecursor of hydride donors are presented. We here report on two new scaffolds along with their photoreactivity in solution. Through use of selected external oxidants, the photogeneration of hydride donors is monitored using UV−visible, NMR, and TEM methods. As a proof-ofconcept, photogeneration of hydride in the presence of Ag + gave rise to the formation of Ag nanoparticles.

Photochromic Diarylethenes Designed for Surface Deposition: From Self‐Assembled Monolayers to Single Molecules

“…Some terarylenes that display thermally-induced release of organic species after subsequent cyclization could be used for both rewritable and non-rewritable memories for photopolymer systems. [103][104][105][106] The reversible o to c isomerization can be used for rewritable memories while the irreversible release of the leaving group could be applied to non-rewritable memory. In addition, the final product in this reaction is an extended planar polyaromatic system important for molecular electronics.…”

Investigations into oxidation induced ring opening of terarylenes containing π-extended thieno[b]thiophene units

“…[3][4][5][6][7][8][9] The properties of photochromic diarylethenes 10,11 and terarylenes 12,13 that photochemically isomerise between open and closed forms, O form and C form, have received considerable interest in recent years. We previously reported the development of terarylene frameworks with ring cyclization quantum yields up to 98% 14 for applications including photoswitches, energy storage 15 and the generation of acids, [16][17][18][19] hydrides 20,21 and Lewis acids. 22 As part of this, we have investigated the ability of some closed form terarylenes to undergo an intermolecular radical cation exchange upon oxidation, leading to a cascade of ring cycloreversion to their O form.…”

Diarylethene Photoswitches Undergoing 6π Azaelectrocyclic Reaction: Disrotatory Thermal Cycloreversion of the Closed-Ring Isomer

“…Namely, it is unclear whether the thermal cycloreversion proceeds via a disrotatory (WH allowed) or conrotatory (WH forbidden) pathway. Moreover, there are few examples of positive utilization of 6π azaelectrocyclic reactions in photochromism. − Therefore, investigation of diarylethene photoswitches undergoing 6π azaelectrocyclic reaction promises a meaningful benefit not only for gaining insight into the dynamics of 6π azaelectrocyclic reaction but also for the further development of novel photochromic diarylethene molecules with new functionality.…”