Phototransformative Supramolecular Assembly of Amphiphilic Diarylethenes Realized by a Combination of Photochromism and Lower Critical Solution Temperature Behavior

Yotsuji, Hajime; Higashiguchi, Kenji; Sato, Ryuma; Shigeta, Yasuteru; Matsuda, Kenji

doi:10.1002/chem.201702202

Cited by 15 publications

(21 citation statements)

References 46 publications

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“…These well-organized crystals exhibit functional morphological changes based on their molecular assembly behavior. [16][17][18][19][20][21][22][23] Similarly, reversible macroscopic transformations of crystals have been reported to date. [24][25][26][27][28]…”

mentioning

confidence: 62%

“…Except for a few examples of chemical oscillation systems, 29,30 stimulus-responsive materials generally repeat their motions in response to an externally controlled stimulus. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] To achieve motion that repeats without external controls, researchers have tried to employ time-delayed cooperative effects. [31][32][33][34][35][36][37][38][39][40] These effects derive from adjustments in the relative direction between energy sources and receptive objects.…”

Section: Sustainable Motionmentioning

confidence: 99%

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Autonomous flipping of azobenzene assemblies under light irradiation (II)

Kageyama

Ikegami²,

Satonaga³

et al. 2020

Preprint

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<p>To create autonomous microrobots which move in the presence of a constant energy source, their mechanical motion must have a capacity for self-control. This is realized when a structural change occurs with conversion of energy facilitated by cofactors, with a self-regulation component to prevent reaching a static state. Here, we present a single crystal structure analysis of azobenene derivatives which reveals a mille-feuille-like layered structure of sparse and dense layers of six independent azobenzene moieties. In this anisotropic structure, a specific azobenzene molecule acts as a reaction center for a light-to-mechanical function process. The other molecules in the crystal act as modulators. Moreover, depending on the photoisomerisation process activated by a polarized light source, different cyclic motions are observed. We clarify the mechanism by which the self-organized mechanical behavior of these azobenzene molecules is achieved at the molecular level. Thus, the present results demonstrate that autonomously driven molecular materials can exhibit information-responsive and self-sustainable motion by incorporating stimulus-responsive sensors. </p>

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mentioning

confidence: 62%

Section: Sustainable Motionmentioning

confidence: 99%

Autonomous flipping of azobenzene assemblies under light irradiation (II)

Kageyama

Ikegami²,

Satonaga³

et al. 2020

Preprint

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“…In later research, they reported micrometer‐sized supramolecular assemblies formed by modifying amphiphilic DAE with octyloxycarbonyl and N‐octylcarbamoyl groups. [ 261 ] In water, spherical assemblies with coacervate structures formed from the open forms of ester‐linked DAE and amide‐linked DAE, which have different morphological change modes (Figure 12d). Those microspheres turned blue immediately under UV irradiation and split under 8 min of continuous irradiation.…”

Section: Changes In the Physical And Chemical Properties Of Daementioning

confidence: 99%

Future‐Oriented Advanced Diarylethene Photoswitches: From Molecular Design to Spontaneous Assembly Systems

et al. 2022

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cycloreversion of DAE under light irradiation produces many exciting functional effects, such as changes in photophysical and photochemical properties, [12] changes in the shape or mechanical properties of the solid, [13] electrical conductivity, [7b,14] and the generation of reactive oxygen species (ROS). [15] This type of photochromic compound can be considered a stilbene derivative. At this time, the most widely known and systematically studied DAE derivative structure contains two aryl groups and a benzene ring (usually two identical or different thiophene units with low aromatic stabilization energy [16] ) and a five-membered ring of perfluorocyclopentene and cyclopentene units [17] where the ethene bridge is located, which significantly improve photochromism. [18] In essence, the DAE photoisomerization process is a reversible electrocyclic reaction of the central 6π-electron systems. [2] Under light irradiation, DAE can rapidly and reversibly transform between its open and closed forms, and that transformation is accompanied by a color change caused by a change in the π-conjugation distribution. [2] The important thing is that the colorless opened-and colored closed-ring isomers are both thermally stable; that is, cyclization and cycloreversion do not proceed spontaneously in the dark; they need to be driven by external light irradiation at specific wavelengths. [2,19] Compared with classic lightresponsive molecules such as azobenzene, [20] the light intensity required to drive the isomerization of DAE is relatively low. Moreover, even after multiple cycles, the photochromic performance does not show significant fatigue in either the solution or solid state. [2,18b,21] DAE research to this point can be roughly divided into three stages in chronological order: early exploration of DAE's molecular structure and theory, nearly two decades of purpose-oriented molecular structure modification research, and about ten years of research into practical applications of DAE in assembly systems. Research before about 2000 focused mainly on developing more abundant DAE-derivative structures and advancing the systematic understanding of DAE's physical and chemical properties and switching performance. To regulate its switching performance and give it new functionality, many strategies for modifying the ethene bridge and aryl groups of DAE have been proposed. [22] In the first two research stages, the mechanisms and structural modification of DAE isomerization were thoroughly and systematically explored, and countless important Diarylethene (DAE) photoswitch is a new and promising family of photochromic molecules and has shown superior performance as a smart trigger in stimulus-responsive materials. During the past few decades, the DAE family has achieved a leap from simple molecules to functional molecules and developed toward validity as a universal switching building block. In recent years, the introduction of DAE into an assembly system has been an attractive strategy that enables the photochromic behavior of the b...

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“…We previously reported triangularshaped amphiphilic diarylethene 2 that is structurally similar to 1 but has only one hydrophobic n-octyloxycarbonyl chain rather than two. [42] The transmission electron microscopy (TEM) image of the assembled triangular-shaped closed-ring isomer 2 b in water revealed its nanostructure to be rod-like micelles. To clearly examine the effect of the nanostructure, the sum of the number of carbon atoms in the alkyl chains of 1 and 2 was set to be the same.…”

Section: Molecular Design and Synthesismentioning

confidence: 99%

“…These results are different from those previously reported for triangular-shaped diarylethene 2. [42] For compound 2, upon irradiation with UV light, the microspheres composed of the open-ring isomer (2 a) turned blue and then divided into smaller microspheres accompanied by the appearance of a redpurple, hazy fringe. This result was interpreted as the phase transition from the high-temperature phase composed of the open-ring isomer (2 a) to the low-temperature phase composed of the open/closed isomer mixture.…”

Section: Macroscopic Morphological Change and Re-entrant Transitionsmentioning

confidence: 99%

Re‐entrant Photoinduced Morphological Transformation and Temperature‐Dependent Kinetic Products of a Rectangular Amphiphilic Diarylethene Assembly

Kotani

Yasuda

Higashiguchi

et al. 2021

Chemistry A European J

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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 temperaturedependent 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.

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Phototransformative Supramolecular Assembly of Amphiphilic Diarylethenes Realized by a Combination of Photochromism and Lower Critical Solution Temperature Behavior

Cited by 15 publications

References 46 publications

Autonomous flipping of azobenzene assemblies under light irradiation (II)

Autonomous flipping of azobenzene assemblies under light irradiation (II)

Future‐Oriented Advanced Diarylethene Photoswitches: From Molecular Design to Spontaneous Assembly Systems

Re‐entrant Photoinduced Morphological Transformation and Temperature‐Dependent Kinetic Products of a Rectangular Amphiphilic Diarylethene Assembly

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