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Enlightening Materials with Photoswitches
Incorporating molecular photoswitches into various materials provides unique opportunities for controlling their properties and functions with high spatiotemporal resolution using remote optical stimuli. The great and largely still untapped potential of these photoresponsive systems has not yet been fully exploited due to the fundamental challenges in harnessing geometrical and electronic changes on the molecular level to modulate macroscopic and bulk material properties. Herein, progress made during the past decade in the field of photoswitchable materials is highlighted. After pointing to some general design principles, materials with an increasing order of the integrated photoswitchable units are discussed, spanning the range from amorphous settings over surfaces/interfaces and supramolecular ensembles, to liquid crystalline and crystalline phases. Finally, some potential future directions are pointed out in the conclusion. In view of the exciting recent achievements in the field, the future emergence and further development of light-driven and optically programmable (inter)active materials and systems are eagerly anticipated. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Imine-Based Dynamic Polymer Networks as Photoprogrammable Amine Sensing Devices
Here, we describe a “smart” polymeric material, which is able to readily detect and discriminate amine vapors. The dynamic imine-based network can be conveniently prepared by mixing a commercially available, amino-functionalized polysiloxane with small amounts of a diarylethene dialdehyde. The photoswitchable crosslinker allows for reversible imprinting of custom-designed patterns on the polymer surface with (sun)light and thus enables noninvasive information storage in the material, which before, during, and after amine exposure can readily be decoded with commonly used smartphone apps. This feature along with the self-healing nature of the dynamic polymer, an easy recycling and manufacturing procedure, and the overall low cost and toxicity render this material advantageous to develop low-cost and practical amine sensing devices for the broad public. © 2019 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2378–2382
Graphene transistors for real-time monitoring molecular self-assembly dynamics
Mastering the dynamics of molecular assembly on surfaces enables the engineering of predictable structural motifs to bestow programmable properties upon target substrates. Yet, monitoring self-assembly in real time on technologically relevant interfaces between a substrate and a solution is challenging, due to experimental complexity of disentangling interfacial from bulk phenomena. Here, we show that graphene devices can be used as highly sensitive detectors to read out the dynamics of molecular self-assembly at the solid/liquid interface in-situ. Irradiation of a photochromic molecule is used to trigger the formation of a metastable self-assembled adlayer on graphene and the dynamics of this process are monitored by tracking the current in the device over time. In perspective, the electrical readout in graphene devices is a diagnostic and highly sensitive means to resolve molecular ensemble dynamics occurring down to the nanosecond time scale, thereby providing a practical and powerful tool to investigate molecular self-organization in 2D. © 2020, The Author(s).
Tunable Photomechanics in Diarylethene-Driven Liquid Crystal Network Actuators
The response of soft actuators made of stimuli-responsive materials can be phenomenologically described by a stimulus-deformation curve, depicting the controllability and sensitivity of the actuator system. Manipulating such stimulus-deformation curve allows fabricating soft microrobots with reconfigurable actuation behavior, which is not easily achievable using conventional materials. Here, we report a light-driven actuator based on a liquid crystal polymer network containing diarylethene (DAE) photoswitches as cross-links, in which the stimulus-deformation curve under visible-light illumination is tuned with UV light. The tuning is brought about by the reversible electrocyclization of the DAE units. Because of the excellent thermal stability of the visible-absorbing closed-form DAEs, the absorbance of the actuator can be optically fixed to a desired value, which in turn dictates the efficiency of photothermally induced deformation. We employ the controllability in devising a logical AND gate with macroscopic output, i.e., an actuator that bends negligibly under UV or visible light irradiation, but with profound shape change when addressed to both simultaneously. The results provide design tools for reconfigurable microrobotics and polymer-based logic gating. © 2020 American Chemical Society. All rights reserved.
Optical and chemical control of the wettability of nanoporous photoswitchable films
Wettability is a central surface property of functional thin films. Here, we present a nanoporous film made of an azobenzene-containing metal-organic framework material where the wettability is controlled by photoswitching of the fluorinated azobenzene moieties and by reversible incorporation of guest molecules with different polarities in the pores. Using both, the optical and the chemical stimuli, the water contact angle was modified over a wide range, from 23° to 97°.
Using Active Surface Plasmons in a Multibit Optical Storage Device to Emulate Long-Term Synaptic Plasticity
Artificial intelligence takes inspiration from the functionalities and structure of the brain to solve complex tasks and allow learning. Yet, hardware realization that simulates the synaptic activities realized with electrical devices still lags behind computer software implementation, which has improved significantly during the past decade. Herein, the capability to emulate synaptic functionalities by exploiting surface plasmon polaritons (SPPs) is shown. By depositing photochromic switching molecules (diarylethene) on a thin film of gold, it is possible to reliably control the electronic configuration of the molecules upon illumination cycles with UV and visible light. These reversible changes modulate the dielectric function of the photochromic film and thus enable the effective control of the SPP dispersion relation at the molecule/gold interface. The plasmonic device displays fundamental functions of a synapse such as potentiation, depression, and long-term plasticity. The integration of such plasmonic devices in an artificial neural network is deployed in plasmonic neuroinspired circuits for optical computing and data transmission. © 2020 The Authors. Published by Wiley-VCH GmbH
Proton-Gated Ring-Closure of a Negative Photochromic Azulene- Based Diarylethene
Proton-responsive photochromic molecules are attractive for their ability to react on non-invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero-atoms, which are orthogonal to the photo-active π-center. Here, we incorporate azulene, an acid-sensitive pure hydrocarbon, into the skeleton of a diarylethene-type photoswitch. The latter exhibits a novel proton-gated negative photochromic ring-closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero-atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its π-system, supported by 1H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non-alternant hydrocarbons into photochromic systems for the development of multi-responsive molecular switches. © 2020 The Authors. Published by Wiley-VCH GmbH
Mechanistic Insights into the Triplet Sensitized Photochromism of Diarylethenes
Operating photoswitchable molecules repetitively and reliably is crucial for most of their applications, in particular in (opto)electronic devices, and related to reversibility and fatigue resistance, which both critically depend on the photoisomerization mechanism defined by the substitution pattern. Two diarylethene photoswitches bearing biacetyl triplet sensitizers either at the periphery or at the core were investigated using both stationary as well as transient UV/Vis absorption spectroscopy ranging from the femtosecond to the microsecond time scale. The diarylethene with two biacetyl moieties at the periphery is switching predominantly from the triplet excited state, giving rise to an enhanced fatigue resistance. In contrast, the diarylethene bearing one diketone at the photoreactive inner carbon atom cyclizes from the singlet excited state and shows significantly higher quantum yields for both cyclization and cycloreversion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Modulating the luminance of organic light-emitting diodes: Via optical stimulation of a photochromic molecular monolayer at transparent oxide electrode
Self-assembled monolayers (SAMs) deposited on bottom electrodes are commonly used to tune charge carrier injection or blocking in optoelectronic devices. Beside the enhancement of device performance, the fabrication of multifunctional devices in which the output can be modulated by multiple external stimuli remains a challenging target. In this work, we report the functionalization of an indium tin oxide (ITO) electrode with a SAM of a diarylethene derivative designed for optically control the electronic properties. Following the demonstration of dense SAM formation and its photochromic activity, as a proof-of-principle, an organic light-emitting diode (OLED) embedding the light-responsive SAM-covered electrode was fabricated and characterized. Optically addressing the two-terminal device by irradiation with ultraviolet light doubles the electroluminescence. The original value can be restored reversibly by irradiation with visible light. This expanded functionality is based on the photoinduced modulation of the electronic structure of the diarylethene isomers, which impact the charge carriers' confinement within the emissive layer. This approach could be successfully exploited in the field of opto-communication technology, for example to fabricate opto-electronic logic circuits. © 2020 The Royal Society of Chemistry.
Highly Cooperative Photoswitching in Dihydropyrene Dimers
We present a strategy to achieve highly cooperative photoswitching, where the initial switching event greatly facilitates subsequent switching of the neighboring unit. By linking donor/acceptor substituted dihydropyrenes via suitable π-conjugated bridges, the quantum yield of the second photochemical ring-opening process could be enhanced by more than two orders of magnitude as compared to the first ring-opening. As a result, the intermediate mixed switching state is not detected during photoisomerization although it is formed during the thermal back reaction. Comparing the switching behavior of various dimers, both experimentally and computationally, helped to unravel the crucial role of the bridging moiety connecting both photochromic units. The presented dihydropyrene dimer serves as model system for longer cooperative switching chains, which, in principle, should enable efficient and directional transfer of information along a molecularly defined path. Moreover, our concept allows to enhance the photosensitivity in oligomeric and polymeric systems and materials thereof. © 2020 The Authors. Published by Wiley-VCH GmbH