One-Color Reversible Control of Photochromic Reactions in a Diarylethene Derivative: Three-Photon Cyclization and Two-Photon Cycloreversion by a Near-Infrared Femtosecond Laser Pulse at 1.28 μm

Abstract

One-color control of colorization/decolorization reactions of diarylethene molecules was attained by using nonresonant high-order multiphoton absorption processes with a near-infrared (NIR) femtosecond laser pulse at 1.28 μm with 35 fs full width at half-maximum (fwhm). The intensity of a rather weak laser pulse (<1 nJ/pulse) can induce the simultaneous three-photon absorption leading to the colorization, while much weaker intensity induces two-photon absorption resulting in the decolorization. The spatial patterning concomitant with higher-order multiphoton absorption processes was also demonstrated.

Visible‐Light‐Activated Molecular Switches

“…[84] Importantly,s uch redox-initiated switching processes are not limited by overlapping spectra of the two switching forms,w hich typically yield PSS mixtures,b ut instead they are purely thermodynamically driven and therefore lead to quantitative isomerization. [82] The disappearance/regeneration of c-15 (green spot) under the laser beam was directlyv isualized on an amorphous film of o-15. from atwo-photon absorber fluorophore (TPA-F).…”

“…This feature is accompanied by the drawback that such oxidatively/reductively initiated switching processes only proceed in one direction, that is,f rom the thermodynamically less stable to the more stable (radical) cation/anion species. [82]. The system was embedded in mesoporoussilica nanoparticles together with abioactive compound for delivery to cancer cells.…”

“…While processes involving the simultaneous absorption of two photons are usually investigated, three-photon absorption processes also offer some interesting possibilities,a s demonstrated by Uchida, Irie,M iyasaka, and co-workers ( Figure 9b). [82] By attaching atriphenylamine derivative that promotes multiphoton absorption in direct conjugation to aD AE moiety (compound 15), the authors could use asingle NIR wavelength (l = 1.28 mm) to ring-close and ring-open 15 by varying the intensity of femtosecond Cr:F laser pulses.Athigher intensity,the three-photon process dominates and the open form of 15,w hich absorbs in the UV region, could be closed, while at lower intensity,t he two-photon process takes place thus re-opening c-15,which absorbs light around 650 nm. Thethree-photon cyclization and two-photon cycloreversion could be followed by absorption spectroscopy and was directly observed through the coloration/decoloration of an amorphous film of 15 under the laser beam (Figure 9b).…”

Dual Visible Light‐Triggered Photoswitch of a Diarylethene Supramolecular Assembly with Cucurbit[8]uril

“…Therefore, it is highly imperative to develop visible light‐triggered DAE‐based photochromic derivatives in both directions. To achieve this goal, several strategies mainly through covalently chemical modification have been explored, such as extended π‐electron conjugation, triplet–triplet energy transfer, energy up‐conversion, multiphoton absorption and electron transfer . However, noncovalent supramolecular approach to achieve this function has not been implemented, to the best of our knowledge.…”

Theoretical investigation on remote-control photocycloreversion of dithienylethene driven by azobenzene chromophores

“…Photochromic dithienylethene (DTE) derivatives, which can undergo reversible photoisomerization by appropriate irradiation, have attracted more and more attention due to their wide applications in optical switches and memories, molecular machines, and nano-devices [1][2][3][4][5][6][7][8]. Usually the irradiation light on DTE must properly match the absorption band of its isomers, according to the Grotthuss-Draper law (also called the principle of photochemical activation), which states that only that light which is absorbed by a system can bring about a photochemical change [9].…”