Photoelectric Signal Conversion by Combination of Electron-Transfer Chain Catalytic Isomerization and Photoisomerization on Benzodimethyldihydropyrenes

Abstract

Photochromic benzocyclophanediene showed oxidation-triggered isomerization to form benzodimethyldihydropyrene. The isomerization proceeded via an autocatalytic reaction system, which could be combined with the photochromic nature of the molecule to establish a new photoelectric signal conversion system.

Reactivity of a pyridinium-substituted dimethyldihydropyrene switch under aerobic conditions: self-sensitized photo-oxygenation and thermal release of singlet oxygen

“…Importantly, the properties of this molecule can be finely tuned by chemical functionalization, a feature that has enabled the recent development of very promising DHP-based multi-functional materials and opto-electronic devices. 10,[37][38][39][40][41][42][43][44] We have recently investigated the behavior of 1 (closed isomer as PF 6 salt, Scheme 1) under an inert atmosphere. 45 The presence of the pyridinium substituents on the DHP core has been shown to significantly improve the photoisomerization efficiency in terms of photoconversion rate and to allow a significant decrease of the irradiation energy (from green to red light).…”

Visible‐Light‐Activated Molecular Switches

“…Nowadays,simple dual photochromism, in which (visible) light is used to isomerize the molecule in one direction, while the reverse reaction is induced by an (electrochemically induced) oxidation or reduction step,isquite well established and has been reported for several photoswitch families,s uch as DAEs, [85] dihydropyrenes, [86] and ABs. [84] As pecial case is orthogonal switches,that is,compounds in which one isomerization can only be induced by light, while the reverse reaction can only be triggered electrochemically.S uch an orthogonal switch has been realized by the design of DAE derivative 16 (Figure 10 a), which undergoes electrocyclization upon oxidation (thereby avoiding the use of UV light) and the reverse cycloreversion upon blue light (l = 436 nm) irradiation.…”

Fast and Efficient Oxidative Cycloreversion Reaction of a π‐Extended Photochromic Terarylene

“…Chemical or electrochemical oxidation has attracted attention as an alternative route for the ring‐opening reaction of diarylethenes because it proceeds with high efficiency in an (electro)catalytic manner . The efficiency of the electrocatalytic cycloreversion reaction was first quantitatively estimated for a dithiazolylthiazole (Scheme ; R 1 =R 2 =Me) to be more than 900 % as a net efficiency, and the instantaneous current efficiency reached over 2000 % as a result of the chain reaction shown in Scheme .…”

“…Chemical or electrochemical oxidation hasa ttracted attention as an alternative route for the ring-opening reaction of diarylethenes because it proceeds with high efficiency in an (electro)catalytic manner. [14][15][16][17][18][19][20][21][22] The efficiency of the electrocatalytic cycloreversion reaction was first quantitatively estimated for ad ithiazolylthiazole (Scheme 1; R 1 = R 2 = Me) to be more than 900 %a sanet efficiency,a nd the instantaneous current efficiency reached over 2000 %a saresult of the chain reaction shown in Scheme1. [20] One-electron oxidation of the c-form readily produced the radicalc ation cC + -form, which was spontaneously converted to the radicalc ation oC + -form through an on-photochemical cycloreversion reactionw ith ar ate constant of k 2 = (3.3 AE 0.06) 10 À1 s À1 .T his cycloreversion rate constant was highert han that of the neutral c-form by seven orders of magnitude, [5a] which clearly suggested that the activation energy of the thermalc ycloreversion reactionw as much reduced in the radicalc ation state.…”