Switching Diarylethenes Reliably in Both Directions with Visible Light

Abstract

A diarylethene photoswitch was covalently connected to two small triplet sensitizer moieties in a conjugated and nonconjugated fashion and the photochromic performance of the resulting compounds was investigated.In comparison with the parent diarylethene (without sensitizers) and one featuring saturated linkages, the conjugated photoswitch offers superior fatigue resistance upon visible-light excitation due to effective triplet energy transfer from the biacetyl termini to the diarylethene core. Our design makes it possible to switch diarylethenes with visible light in both directions in a highly efficient and robust fashion based on extending π-conjugation and by-product-free ring-closure via the triplet manifold.

Photochromism and molecular logic gate operation of a water-compatible bis-glycosyl diarylethene

“…1 Because of the sharp difference in physical properties 2 such as optical, 3 electrochemical 4 and geometrical features 5 between the two isomers, photochromic compounds can be used to construct a variety of photoswitchable functional materials including fluorescence probes, 6 molecular logic gates, 7 optical data-storage devices 8 and photoresponsive assemblies. 9 Of the photochromic compounds reported, diarylethenes are viewed as one of the most promising candidates for photo-electronic applications due to their outstanding fatigue-resistance, 10 thermal stability 11 and rapid response towards light. 12 In recent years, the design and synthesis of diarylethene derivatives incorporating fluorophores have been a decent strategy in the rational design of molecular logic gates based on Förster resonance energy transfer (FRET) or photoinduced electron transfer (PET).…”

Electronic Properties of Optically Switchable Photochromic Diarylethene Molecules at the Interface with Organic Semiconductors

“…The fraction of 45% DAE1-o and 55% DAE1-c molecules (see fitting results in inset of Fig 2a) suggests that the back transfer (from DAE1-o to DAE1-c) was not completely reversible. This can be attributed to a manifold of causes, such as steric hindrance, [17,[22][23] radiation (UV, VUV) induced photoquenching, [24] which prohibit such photoswitching of diarylethene molecules during light irradiation. Fully analogous photochromic switching was also observed for an ultrathin DAE1-c layer with only of 2 nm thickness (Fig.…”

“…Therefore, DAE molecules show promising potential due to their high fatigue resistance and thermal bistability. [6,17] Ultraviolet photoemission spectroscopy (UPS) studies on thin films of DAE derivatives revealed a large difference of the ionization energy (IE) between the open and closed isomers of approximately 1 eV. [10] It was reported that this change in IE can be used to alter the current through the channel of organic field effect transistors (OFET) where DAE molecules were blended into the polymeric semiconductor poly(hexylthiophene) (P3HT).…”

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

“…However, the high photocyclization quantum yield comes at a cost of low cycloreversion. Nevertheless, other strategies for cycloreversion are also available: heating, [25] multiphoton absorption, [26] triplet sensitization, [27] and photo/electrocatalytic chain reactions. [28][29][30][31][32][33][34][35][36] Fourth, Irie and Uchida reported a diarylethene based on a benzothiophene where the aromatic groups have high fatigue resistance.…”