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Photomechanical molecular crystals have garnered attention for their ability to transform light into mechanical work, but difficulties in characterizing the structural changes and mechanical responses experimentally have hindered the development of practical organic crystal engines. This study proposes a new computational framework for predicting the solid-state crystal-to-crystal photochemical transformations entirely from first principles, and it establishes a photomechanical engine cycle that quantifies the anisotropic mechanical performance resulting from the transformation. The approach relies on crystal structure prediction, solid-state topochemical principles, and high-quality electronic structure methods. After validating the framework on the well-studied [4 + 4] cycloadditions in 9-methyl anthracene and 9-tert-butyl anthracene ester, the experimentally-unknown solid-state transformation of 9-carboxylic acid anthracene is predicted for the first time. The results illustrate how the mechanical work is done by relaxation of the crystal lattice to accommodate the photoproduct, rather than by the photochemistry itself. The large ∼107 J m-3 work densities computed for all three systems highlight the promise of photomechanical crystal engines. This study demonstrates the importance of crystal packing in determining molecular crystal engine performance and provides tools and insights to design improved materials in silico.

Microcrystals composed of the conjugated organic molecule perylene can be encapsulated beneath single-layer graphene using mild conditions. Scanning electron and atomic force microscopy images show that the graphene exists as a conformal coating on top of the crystal. Raman spectroscopy indicates that the graphene is only slightly perturbed by the underlying crystal, probably due to strain. The graphene layer provides complete protection from a variety of solvents and prevents sublimation of the crystal at elevated temperatures. Time-resolved photoluminescence measurements do not detect any quenching of the perylene emission by the graphene layer, although nonradiative energy transfer within a few nanometers of the crystal-graphene interface cannot be ruled out. The ability to encapsulate samples on a substrate under a graphene monolayer may provide a new way to access and interact with the organic crystal under ambient conditions.

Organic photomechanical crystals transform molecular‐scale photoisomerization events into largescale crystal shape changes. The results in this paper demonstrate that this photomechanical motion can be harnessed to reconfigure reflective elements on the crystal surface to actively control light propagation. This is accomplished by using a single organic photomechanical crystal composed of 1,2‐bis(2,4‐dimethyl‐5‐phenyl‐3‐thienyl)‐3,3,4,4,5,5‐hexafluoro‐1‐cyclopentene, which undergoes a reversible ring‐open to ring‐closed photoisomerization. Electron beam lithography patterning followed by a sublimation development step leaves periodically positioned, 120 nm deep grooves that are coated with gold metal to form a reflective grating on the crystal surface. Under UV irradiation, expansion of the bulk crystal increases the grating period by ≈5% and changes the diffraction angle of a 633 nm probe laser beam by 0.7° (first order) and 1.3° (second order). The grating period change can be reversed by visible light exposure and repeated for multiple cycles. The crystal expansion and thus the diffraction angle can also be continuously tuned by controlling the duration of light exposure. Anisotropic crystal expansion and contraction due to molecular photoisomerization enables low‐power light sources to steer light beams continuously over a range of diffraction angles. [ABSTRACT FROM AUTHOR]

9-Methylanthracene (9MA) undergoes a concerted [4 + 4] photodimerization in its crystal form that can be harnessed in order to generate photomechanical motions such as bending, twisting, and expansion. As described in this paper, 9MA nanowires were grown in anodic aluminum oxide (AAO) templates with the goal of using the crystal expansion to generate a net increase in the height of the composite disk. The growth conditions were optimized in order to raise the filling amount from 28% to 77% of the available volume in the porous AAO. A new experimental method for detecting motion, based on the analysis of data from a dynamically misaligned Michelson interferometer, was developed. Template bending was observed, showing that the photodimerization of the confined nanowires generated mechanical work, but no conclusive evidence for surface disruption or vertical translation was observed. Optical measurements, as well as atomic force and scanning electron microscopy, showed that incomplete filling, crystal orientation, and debris from template polishing likely prevented the observation of vertical actuation in these nanocrystal composites. This work highlights some of the practical challenges that are involved in creating photomechanical actuators using the organic–inorganic composite approach, with the two most significant being (1) the uniform filling of the porous template with the organic active material and (2) the removal of excess organic material from the template's surface. [ABSTRACT FROM AUTHOR]

Hollow organic molecular cocrystals comprised of 9‐methylanthracene‐1,2,4,5‐tetracyanobenzene (9MA‐TCNB) and naphthalene‐1,2,4,5‐tetracyanobenzene (NAPH‐TCNB) were fabricated using a surfactant‐mediated co‐reprecipitation method. The crystals exhibit a narrow size distribution that can be easily tuned by varying the concentration of surfactant and incubation temperature. The rectangular crystals possess symmetrical twinned cavities with an estimated storage volume on the order of 10−10 L. An aqueous dye solution can be incorporated into the cavities during crystal growth and stored inside for up to several hours, confirming the sealed nature of the hollow chambers. Our results demonstrate that it is possible to harness non‐classical crystal growth to fabricate organic molecular crystals with novel topologies. [ABSTRACT FROM AUTHOR]

Improving the modulation depth and switching speed of electrochromic devices is important for expanding the field of electrochromic functional materials applications. The previous study demonstrates that semiconducting (SC‐) single‐wall carbon nanotube (SWNT) thin film based electrochromic cells with ionic liquid as the electrolyte and metallic (MT‐) SWNT counter electrode can operate with fast switching times in the millisecond range. However, achieving a high modulation depth requires an increasing thickness of the electrochromically active SC‐SWNT layer resulting in a slowdown of the switching time by more than order of magnitude. Here it is reported that milliseconds range switching time can be restored by increasing the thickness of MT‐SWNT thin film counter electrode thus matching the electrochemical capacitances of the two sides of the electrochromic cell while reaching a high modulation depth of 20 dB and high coloration efficiency exceeding 1800 cm2 C−1 at an infrared wavelength of 1770 nm. The results are interpreted in terms of considering the SWNT cell as a supercapacitor with two connected in series electric double layer 3D capacitors associated with two opposing SWNT electrodes. Fast operation of single‐wall carbon nano‐tube (SWNT) electrochromic device is achieved for high thicknesses of electrochromically active semiconducting SWNT films by increasing thickness of metallic SWNT counter electrode to match electrochemical capacitances of both electrodes. The balanced device shows modulation depth of 20 dB, millisecond range response time, and coloration efficiency exceeding 1800 cm2 C−1 at infrared wavelength 1770 nm. [ABSTRACT FROM AUTHOR]

We report the experimental realization of η 6 -complexes of group 6 transition metals with a single layer graphene using photo-activated reactions with organometallic compounds. The reaction progress was followed by in-situ measurements of the graphene conductivity. We observed that the chromium reagents exert the strongest effect on the electronic properties of graphene, leading to (η 6 -graphene)CrL [L = C 6 H 6 , (CO) 3 ] complexes with enhanced conductivity. Thus, in the case of covalent functionalization of graphene with Cr(CO) 6 , the conductivity increased by a factor of 4, while the (η 6 - C 6 H 6 )Cr(CO) 3 reagent doubled the conductivity producing the least enhancement. This mode of covalent bonding preserves the conjugation and the planarity of the graphene structure and offers a promising route for the preparation of a new class of graphitic materials functionalized with transition metals, which may find applications in optoelectronics, spintronics and magnetic nanodevices. [ABSTRACT FROM AUTHOR]

CVD graphene has attracted a great deal of interest from both academia and industry. The strong motivation to commercialize high quality CVD graphene films and related devices has been restricted by the lack of a cheap, efficient, clean and reliable graphene transfer process. In this article, we report a novel graphene transfer technique which provides a route to high-throughput, reliable and economical transfer of graphene without introducing large cracks and residue contamination from polymers, such as PMMA or magnetic impurities. The transferred graphene was thoroughly characterized with Raman spectroscopy, Atomic Force Microscopy, and X-ray photoelectron spectroscopy. Fabricated large area graphene-based field effect transistors exhibited high mobilities, which were about 2 times higher than those for devices prepared with graphene transferred by the conventional wet transfer method. This new graphene transfer technique has the potential to expedite the large scale industrial utilization of CVD graphene in electronics, spintronics, catalysis and energy storage. [ABSTRACT FROM AUTHOR]

Converting biomass waste into high-value products presents a challenging task in the environmental field. Growth of graphene from solid-state precursors is cost-effective and is becoming a hot research topic. However, the underlying mechanisms are as yet unclear. In this work, we report a novel method for directly growing adlayer-free large area graphene from cellulose acetate, the main component of cigarette filter waste. The evolution of cellulose acetate to reduced graphene oxide and finally to graphene is shown in this work for the first time. The effect of various growth parameters, hydrogen concentration and Cu grain boundaries on the size and qualities of the monolayer graphene domains is clarified. Finally, the mechanism for the growth of graphene from a solid-state precursor is proposed. The field-effect-transistor fabricated from transferred monolayer graphene demonstrated high electron and hole mobilities ∼1500 cm2/(V·s). This work presents a new opportunity for converting biomass waste into high-value graphene products. Image 1 [ABSTRACT FROM AUTHOR]

Photomechanical molecular crystals have garnered attention for their ability to transform light into mechanical work, but difficulties in characterizing the structural changes and mechanical responses experimentally have hindered the development of practical organic crystal engines. This study proposes a new computational framework for predicting the solid-state crystal-to-crystal photochemical transformations entirely from first principles, and it establishes a photomechanical engine cycle that quantifies the anisotropic mechanical performance resulting from the transformation. The approach relies on crystal structure prediction, solid-state topochemical principles, and high-quality electronic structure methods. After validating the framework on the well-studied [4 + 4] cycloadditions in 9-methyl anthracene and 9- tert -butyl anthracene ester, the experimentally-unknown solid-state transformation of 9-carboxylic acid anthracene is predicted for the first time. The results illustrate how the mechanical work is done by relaxation of the crystal lattice to accommodate the photoproduct, rather than by the photochemistry itself. The large ∼10 7 J m -3 work densities computed for all three systems highlight the promise of photomechanical crystal engines. This study demonstrates the importance of crystal packing in determining molecular crystal engine performance and provides tools and insights to design improved materials in silico ., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Lithography methods are commonly used to create structures in inorganic semiconductors like silicon but have not been widely applied to organic crystals. In this work, electron beam lithography (EBL) is used to pattern structures into single organic photomechanical crystals composed of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene. The electron beam creates amorphous regions of decomposed molecules, while the reactivity of the unexposed crystal regions is preserved under a removable Au coating. Exposure of the patterned crystal to 365 nm light causes ridges of amorphous material to increase in height by 30-70%. This height increase can be reversed by visible light exposure and undergo multiple cycles. The reversible surface morphology changes are strong enough to rupture a sheet of graphene placed on top of the patterned crystal. Surprisingly, the change in dimensions of the EBL features is an order of magnitude larger than the changes in overall crystal dimensions as deduced from X-ray diffraction experiments and microscopy observations. A dynamic extrusion model is presented to explain how nanoscale features imprinted into single crystals can amplify molecular-level photomechanical changes. This work demonstrates the capability of EBL methods to produce sub-micron structural features on single photomechanical crystals, providing a new route to monolithic light-powered actuator devices.

Advances in the chemical vapor deposition (CVD) growth of graphene have made this material a very attractive candidate for a number of applications including transparent conductors, electronics, optoeletronics, biomedical devices and energy storage. The CVD method requires transfer of graphene on a desired substrate and this is most commonly accomplished with polymers. The removal of polymer carriers is achieved with organic solvents or thermal treatment which makes this approach inappropriate for application to plastic thin films such as polyethylene terephthalate substrates. An ultraclean graphene transfer method under mild conditions is highly desired. In this article, we report a naphthalene-assisted graphene transfer technique which provides a reliable route to residue-free transfer of graphene to both hard and flexible substrates. The quality of the transferred graphene was characterized with atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. Field effect transistors, based on the naphthalene-transfered graphene, were fabricated and characterized. This work has the potential to broaden the applications of CVD graphene in fields where ultraclean graphene and mild graphene transfer conditions are required.