Toward optomechanics: Maximizing the photodeformation of individual molecules

Bléger, David; Yu, Zhilin; Hecht, Stefan

doi:10.1039/c1cc15180k

Cited by 115 publications

(108 citation statements)

References 57 publications

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“…Illumination of these materials can induce actuation over large length scales, beginning with the molecular-scale photoisomerization process 1,2 and emerging into visually observable macroscopic motions. Illumination of these materials can induce actuation over large length scales, beginning with the molecular-scale photoisomerization process 1,2 and emerging into visually observable macroscopic motions.…”

Section: Introductionmentioning

confidence: 99%

From partial to complete optical erasure of azobenzene–polymer gratings: effect of molecular weight

et al. 2015

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The ability to control surface functionality by optical inscription and erasure of surface patterns is highly appealing, since it opens up the possibility for the design of complex, spatially varying surface topographies. We show through a supramolecular approach, which allows us to attach nominally equal amounts of azobenzene into polymers of varying molecular weight, that the completeness of optical erasure of high-modulation-depth surface-relief gratings on polymer-azobenzene complexes depends on the molecular weight of the polymer, and therefore on the glass transition temperature of the material used. The optical erasure is further applied to realize surface patterns with varying grating vector directions through masking. All patterning is done at a temperature well below the glass transition temperatures of the materials, which allows different patterning steps to be frozen into the material. Fig. 3 Scanning electron microscopy images of surface patterns with spatially varying grating vector directions, created by first optically erasing the SRG in non-masked areas (where masking was accomplished by placing a transmission electron microscope grid onto a previously inscribed SRG) and then inscribing another SRG perpendicular to the original one through the mask.

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Section: Introductionmentioning

confidence: 99%

From partial to complete optical erasure of azobenzene–polymer gratings: effect of molecular weight

et al. 2015

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“…The E → Z photoisomerization of azobenzene derivatives is well documented for azobenzenecontaining polymers 18 , liquid crystals 9,18-24 , thin films [25][26][27] and crystals at the solid-liquid interface 28 , and a limited number of examples are reported in porous materials [29][30][31][32][33] (for example, metal-organic and covalent organic frameworks) and in molecular crystalline forms in which the azobenzene moiety is functionalized with polar substituents [34][35][36] . Our strategy is based on the use of molecules containing a central node that imparts a star-like threedimensional arrangement to azobenzene moieties for the fabrication of molecular crystals endowed with permanent porosity capable of promoting reversible E/Z isomerization in the solid state.…”

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confidence: 99%

Photoinduced reversible switching of porosity in molecular crystals based on star-shaped azobenzene tetramers

et al. 2015

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The development of solid materials that can be reversibly interconverted by light between forms with different physico-chemical properties is of great interest for separation, catalysis, optoelectronics, holography, mechanical actuation and solar energy conversion. Here, we describe a series of shape-persistent azobenzene tetramers that form porous molecular crystals in their E-configuration, the porosity of which can be tuned by changing the peripheral substituents on the molecule. Efficient E→Z photoisomerization of the azobenzene units takes place in the solid state and converts the crystals into a non-porous amorphous melt phase. Crystallinity and porosity are restored upon Z→E isomerization promoted by visible light irradiation or heating. We demonstrate that the photoisomerization enables reversible on/off switching of optical properties such as birefringence as well as the capture of CO2 from the gas phase. The linear design, structural versatility and synthetic accessibility make this new family of materials potentially interesting for technological applications.

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“…In particular, when these molecules are orderly supported on a surface, they can express a considerable mechanical work that allows the execution of light-propelled actions at the nanoscale [4][5][6]. Molecular rods containing the azobenzene moiety (4 0 -{[(1,1 0 -biphenyl)-4-yl]diazenyl}-(1,1 0 -biphenyl)-4-thiol, thio-2-DA in the following) and supported on gold surfaces have been found to be optically and reversibly switchable with high yield from trans to cis and back [4,5,7].…”

Section: Introductionmentioning

confidence: 99%

First-principle-based MD description of azobenzene molecular rods

et al. 2012

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Extensive density functional theory (DFT) calculations have been performed to develop a force field for the classical molecular dynamics (MD) simulations of various azobenzene derivatives. Besides azobenzene, we focused on a thiolated azobenzene's molecular rodthat has been previously demonstrated to photoisomerize from trans to cis with high yields on surfaces. The developed force field is an extension of OPLS All Atoms, and key bonding parameters are parameterized to reproduce the potential energy profiles calculated by DFT. For each of the parameterized molecule, we propose three sets of parameters: one best suited for the trans configuration, one for the cis configuration, and finally, a set able to describe both at a satisfactory degree. The quality of the derived parameters is evaluated by comparing with structural and vibrational experimental data. The developed force field opens the way to the classical MD simulations of selfassembled monolayers (SAMs) of azobenzene's molecular rods, as well as to the quantum mechanics/molecular mechanics study of photoisomerization in SAMs.

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Toward optomechanics: Maximizing the photodeformation of individual molecules

Cited by 115 publications

References 57 publications

From partial to complete optical erasure of azobenzene–polymer gratings: effect of molecular weight

From partial to complete optical erasure of azobenzene–polymer gratings: effect of molecular weight

Photoinduced reversible switching of porosity in molecular crystals based on star-shaped azobenzene tetramers

First-principle-based MD description of azobenzene molecular rods

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