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Amphiphilic diarylethene with tri(ethylene glycol) chains as a hydrophilic moiety and octylcarbamoyl chain as a hydrophobic moiety formed a supramolecular assembly by hydrophobic interactions in wa...

Ambipolar carrier transport is demonstrated in an optically controllable organic field-effect transistor, where a benzothienothiophene-substituted diarylethene (BTT-DAE) thin film is employed directly as the transistor channel. A closed-ring isomer, which is produced by ultraviolet (UV) light irradiation, allows the carrier injection of both holes and electrons from source-drain electrodes into the BTT-DAE layer. Moreover, alternate UV or visible (VIS) light irradiation induces marked switching in the drain currents caused by reversible photoisomerization between closed-ring (semiconductor) and open-ring (insulator) isomers. The light-driven on/off ratio, which is defined by the ratio of the drain currents in the sample after UV or VIS light irradiation, reaches 240 for hole transport. The value is comparable to the gate-voltage-induced on/off ratio of 160. Our findings, therefore, have a potential to lead to the construction of new optoelectronic devices such as photoreconfigurable logic circuits and light emitting transistors.

An amphiphilic rectangular-shaped photochromic diarylethene bearing two hydrophobic alkyl chains and two hydrophilic tri(ethylene glycol) chains was synthesized, and its photoinduced morphological transformation in water was investigated. Two unexpected phenomena were revealed in the course of the experiments: a re-entrant photoinduced macroscopic morphological transformation and temperature-dependent kinetic products of supramolecular assembly. When the pure closed-ring isomer was dispersed in water, a re-entrant photoinduced morphological transformation, that is, a photoinduced transition from the hydrated phase to the dehydrated phase and then back to the hydrated phase, was observed by optical microscopy upon irradiation with green light at 20 °C; this was interpreted by the V-shaped phase diagram of the LCST transition. The aqueous assembly of the pure closed-ring isomer was controlled by changing the temperature; specifically, rapid cooling to 15 and 5 °C gave J and H aggregates, respectively, as the kinetic products. The thermodynamic product at both temperatures was a mixture of mostly H aggregate with a small amount of J aggregate. This behavior was rationalized by the temperature-dependent potential energy surface of the supramolecular assembly.

Bis(imino nitroxide) bridged by a diarylethene annulated isomer was synthesized and the exchange interaction between the two radicals was determined by the simulation of the ESR spectrum. The exchange interaction was found to be as large as that of the closed-ring isomer, suggesting that the annulated isomer can be used as a highly-conductive molecular wire in molecular electronics.

Self-assembly of amphiphilic photochromic diarylethene having tri(ethylene glycol) monomethyl ether chains was examined in water from the viewpoint of photoinduced morphological transformation and photodriven movement of objects. Self-assembled supramolecular architectures of the amphiphilic diarylethenes undergo photoinduced macroscopic morphological transformation upon alternate irradiation with UV and visible light. The photoreversible morphological change can be rationalized as a photoinduced phase transition between the high- and low-temperature phases of the lower critical solution temperature (LCST) transition. By using a depletion force in a methylcellulose aqueous solution, an amphiphilic diarylethene hierarchically assembled into bundled fibers, which showed shrinking of more than 100 μm under visible light irradiation. Linearly polarized light induced anisotropic growth of the assembled architecture and the diffusive motion of added polystyrene beads was suppressed in the perpendicular direction to the polarized light. The movement of many objects tracing the movement of a UV-irradiation spot was achieved with the assistance of the photogenerated supramolecular architecture.

Amphiphilic diarylethenes bearing octyloxycarbonyl and N-octylcarbamoyl groups have been designed and synthesized. These ester- and amide-linked compounds form micrometer-sized supramolecular assemblies in water, and these assemblies exhibit photoinduced macroscopic morphological transformations upon alternate irradiation with UV and visible light. The ester-linked diarylethene showed a transformation between colorless spheres and a red-purple hazy fringe, whereas the microspheres of the amide-linked diarylethene showed changes in color, size, and shape, but the spheres did not show division. TEM images revealed that the spheres of the open-ring isomers have coacervate structures, with bicontinuous aqueous and organic phases. The closed-ring isomers of the ester- and amide-linked compounds were found to form nanofibers and thin layers, respectively. These compounds showed absorption spectral shifts at temperatures corresponding to the lower critical solution temperature (LCST) transition. This morphological transformation can be rationalized as the photoinduced phase transition between the high- and low-temperature phases of the LCST transition. These results open up a new avenue for the design of phototransformative supramolecular assemblies based on a combination of photochromism and LCST behavior.

Photoinduced clustering of polystyrene microbeads and photocontrol of their diffusion was achieved in water with the assistance of photoinduced transformation of supramolecular architecture of amphiphilic diarylethene between sphere and fiber states. When a suspension of polystyrene beads containing the sphere state of diarylethene was UV-irradiated from beneath, clustering of the polystyrene beads by thermal convection was observed. The velocity of clustering was dependent on the amount of photogenerated nanofibers that determines the viscosity of the water. Diffusion of the clustered polymer beads was suppressed by the surrounding fibers, but was restored to regular Brownian motion upon irradiation with visible light. It was suggested that the diffusion of the microbeads was controlled by the transformation of aggregates between the more viscous fiber state and the less viscous sphere state. These results provide new insight into the photocontrol of particle motion in fluidic media.

A supramolecular assembly composed of a two-component mixture of amphiphilic diarylethenes, which have octyloxycarbonyl and N-octylcarbamoyl groups, showed a unique macroscopic transformation upon irradiation with UV light and subsequent standing in the dark. Unlike the pure compounds, the assembly was repetitively separated into a blue sphere and a red-purple sparse structure. Both the blue sphere and the sparse structure turned into colorless spheres upon irradiation with visible light and the divided colorless spheres showed the same response to UV and visible light. Phase diagrams based on the change in absorption spectra upon temperature change suggested that the transformation originates from a LCST transition. In the 0.5 : 0.5 mixture, in contrast to the pure compounds, the transition temperature sharply changed at around 50% of the fraction of the closed-ring isomer. TEM imaging showed that the 0.5 : 0.5 mixture with high photoisomerization yield formed a 10 nm-sized network. Judging from the phase diagram and TEM images, the separation is understood as the local phase transition of the regions with a high fraction of the closed-ring isomer.

Optical switching organic field-effect transistors (OFETs) provide a new direction for optoelectronics based on photochromic molecules. However, the patterning of OFETs is difficult because conventional fabrication processes, including lithography and ion etching, inevitably cause severe damage to organic molecules. Here, we demonstrate laser patterning of one-dimensional (1D) channels on an OFET with a photochromic diarylethene (DAE) layer. The main findings are (i) a number of 1D channels can be repeatedly written and erased in the DAE layer by scanning focused ultraviolet and visible light laser beams alternately between the source and drain electrodes, (ii) the conductivity (or resistivity) of the 1D channel can be controlled by the illumination conditions, such as the laser power density and the scan speed, and (iii) it is possible to draw an analogue adder circuit by optically writing 1D channels so that a portion of the channels overlaps and to perform optical summing operations by local laser illumination of the respective channels. These findings will open new possibilities for realizing various optically reconfigurable, low-dimensional organic transistor circuits, which are not possible with conventional thin film OFETs.

Quantum yields can be determined by global fitting of prolonged change of concentration against absorbed photon numbers. Quantum yields of synthesized amphiphilic diarylethene in solution and in suspension were analyzed by the global fitting upon irradiation with UV (365 nm) light. Quantum yields of cyclization and cycloreversion reaction in acetonitrile were obtained as 0.59 and 0.013, respectively using the absolute method. In suspension, quantum yield of cyclization was determined as 0.76 using the relative method. The result indicates that the preferred conformation of the open-ring isomer in the aggregate was antiparallel due to the hydrophilic chains and hydrogen bond.

Self-assembled microstructures of an amphiphilic diarylethene featuring an alkyl chain and triethylene glycol groups showed a photoinduced reversible morphological change in water. Reversible photoisomerization of the core diarylethene gave rise to a reversible morphological transformation between colorless microspheres and colored fibers. When colorless microspheres were irradiated with UV light, colored fibers were formed, and when the colored fibers were irradiated with visible light, the spheres were restored to their original positions where the spheres originally existed. This system showed reversible morphological change through not only photoirradiation but also temperature change. These behaviors can be interpreted as a phase transition between the sphere and fiber states. The dynamic process of the phase transition was monitored by polarized optical microscopy (POM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). It was revealed that the formation of fibers upon UV irradiation occurred radially at the surface of the sphere and the formation of the spheres upon visible-light irradiation occurred at the middle of the fiber. The unique photoinduced mechanical motion provides useful information for the design of sophisticated photoactuators.

We demonstrated optical manipulation of single-electron tunneling (SET) by photoisomerization of diarylethene molecules in a metal-insulator-semiconductor (MIS) structure. Stress is placed on the fact that device operation is realized in the practical device configuration of MIS structure and that it is not achieved in structures based on nanogap electrodes and scanning probe techniques. Namely, this is a basic memory device configuration that has the potential for large-scale integration. In our device, the threshold voltage of SET was clearly modulated as a reversible change in the molecular orbital induced by photoisomerization, indicating that diarylethene molecules worked as optically controllable quantum dots. These findings will allow the integration of photonic functionality into current Si-based memory devices, which is a unique feature of organic molecules that is unobtainable with inorganic materials. Our proposed device therefore has enormous potential for providing a breakthrough in Si technology.

Diarylethenes, which have same core structures but have different positions of thiol groups that are bound to gold nanoparticles, were prepared. In one diarylethene, which has two thiol groups at the positions equivalent to 5,5′-positions of di(3-thienyl)ethene, the π-connectivity between two thiol groups increases upon photocyclization, but in the other diarylethene, which has two thiol groups at 2- and 5-positions of one of the 3-thenyl group, the π-connectivity decreases upon photocyclization. The gold nanoparticle networks of these diarylethenes were prepared and the change in conductance was measured upon alternate irradiation with UV and visible light. For two diarylethenes, the direction of the photoswitching was opposite, reflecting the difference in the π-connectivity. The result suggests that the topology of π-conjugation between electrodes is the decisive factor in the conductance of gold nanoparticle network.

International audience; Photochromic diarylethene (DAE) molecules were employed as the channel layer of a field-effect transistor, where the drain current was effectively modulated by the reversible phase transition between a semiconductor (closed-ring) and an insulator (open-ring) under ultraviolet or visible light irradiation. Our goal was the further improvement of optical switching properties by interface engineering. First, we reduced the hole injection barrier by introducing an a -sexithiophene (6T) thin film at the interface between the source–drain electrodes and the DAE channel layer. As a result, the threshold voltage of the DAE-FETs was greatly reduced from -64 to -4 V. Second, we improved the optical switching performance by the surface treatment of a SiO 2 gate insulator with poly(methyl methacrylate) (PMMA). The drain current was unchanged even after 10 cycles of optical switching in contrast to the rapid degradation found with untreated DAE transistors. The combination of these improvements and interdigitated source–drain electrodes eventually resulted in a light irradiation driven on/off ratio of over 10^3. Significantly, the light-induced on/off ratio was comparable to that driven by an electrical field, which satisfies the requirement for industrial optical applications. Our findings will provide useful ways of realizing high-performance optical switching transistors.

A substituent effect of asymmetric diarylethene annulated isomer on their chiroptical properties was investigated by means of theoretical and experimental approaches. The absolute configuration of the annulated isomer was determined by X-ray structural analysis and DFT calculation. The TD–DFT calculation successfully reproduced not only the sign but also the shape and magnitude of experimental CD spectrum by considering the Boltzmann-weighted average of four atrop-isomers. A fragment decomposition (FD) analysis of rotatory strength clearly revealed a noteworthy effect; the tilting motion concomitant with the rotating motion of the substituent affects the sign and magnitude of CD signals. It was found that even when the absolute structure of the chiral core moiety does not change, the slight motion of the substituent can trigger the inversion of the CD signal.

We achieved drain-current switching of diarylethene-channel field-effect transistors with light- and electric-field effects. The drain current was reversibly changed by alternating ultraviolet and visible light irradiation. Stress is placed on the fact that the on/off ratio realized by light irradiation was 1 × 10(2) (1 × 10(4)%) and this value is much larger than those in other photochromism-based transistors. These results indicate that the drain current was effectively controlled by light irradiation. Furthermore, the on and off states modulated by light were maintained without light irradiation even after 1 week, exhibiting that our transistor works as an optical memory. We clarified that the light-driven modulation can be attributed to the transformation in the π-conjugation system accompanied by photoisomerization. These findings have the potential to attain high-performance optoelectrical organic devices including optical sensors, optical memory, and photoswitching transistors.

Unusual blue shift of the absorption maxima of two nitronyl nitroxide attached diarylethene through phenyl units (DAE-phe-NN) with increasing number of phenyl units is examined by time dependent density functional theory (TDDFT). The extended π-conjugation between nitronyl nitroxide and diarylethene is rather suppressed by the bridge phenyl units. In comparison, the red shift found in two nitronyl nitroxide attached diarylethenes through thiophene units (DAE-thio-NN) with increasing number of thiophene units is due to the longer π-conjugation induced by smaller dihedral angles between diarylethene and bridge and between bridges.

A diarylethene fused trimer, 1-(5-(2-(3,5-dimethyl-2-thienyl)hexafluorocyclopententen-1-yl)-2,4-dimethyl-3-thienyl)-2-(5-(2-(2,4-dimethyl-5-phenyl-3-thienyl)hexafluorocyclopentene-1-yl)-2,4-dimethyl-3-thienyl)hexafluorocyclopentene, was synthesized. The diarylethene derivative showed full-color photochromic performance by choosing appropriate wavelength of light.