Bridging photochemistry and photomechanics with NMR crystallography: the molecular basis for the macroscopic expansion of an anthracene ester nanorod

Chalek, Kevin; Dong, Xinning; Tong, Fei; Kudla, Ryan A.; Zhu, Lingyan; Gill, Adam D.; Xu, Wenwen; Yang, Chen; Hartman, Joshua D.; Magalhães, Alviclér; Al‐Kaysi, Rabih O.; Hayward, Ryan C.; Hooley, Richard J.; Beran, Gregory J. O.; Bardeen, Christopher J.; Mueller, Leonard J.

doi:10.1039/d0sc05118g

Cited by 27 publications

(25 citation statements)

References 95 publications

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“…[43,48] It seems that solid-state dimerization leads to adifferent dimer crystal polymorph, as observed in other anthracene derivatives. [49] In the Supporting Information, we present solid-state NMR data that is consistent with this possibility,but since the current paper focuses on the reaction dynamics,d etailed characterization of the crystal produced by solid-state photodimerization must be reserved for future work. Eventually, the quantitative prediction of the crystal expansion/contraction will require precise determination of this crystal packing and orientation.…”

Section: Methodsmentioning

confidence: 85%

Correlating Reaction Dynamics and Size Change during the Photomechanical Transformation of 9‐Methylanthracene Single Crystals

et al. 2021

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Photomechanical molecular crystals that expand under illumination could potentially be used as photonpowered actuators.I nt his study,w ef ind that the use of highquality single crystals of 9-methylanthracene (9MA)l eads to more homogeneous reaction kinetics than that previously seen for polycrystalline samples,p resumably due to al ower concentration of defects.F urthermore,s imultaneous observation of absorbance and shape changes in single crystals revealed that the dimensional change mirrors the reaction progress, resulting in asmooth expansion of 7% along the c-axis that is linearly correlated with reaction progress.The same expansion dynamics are highly reproducible across different single crystal samples.O rganic single crystals exhibit well-defined linear expansions during 100 %photoconversion, suggesting that this class of solid-state phase change material could be used for actuation.

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Section: Methodsmentioning

confidence: 85%

Correlating Reaction Dynamics and Size Change during the Photomechanical Transformation of 9‐Methylanthracene Single Crystals

et al. 2021

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“…NMR parameters derived from the CS and EFG tensors have been used extensively in molecular structure refinement (Olsen et al, 2003;Witter et al, 2006;Harris et al, 2010;Apperley et al, 2012;Harper et al, 2013;Kalakewich et al, 2015;Yang et al, 2016;Soss et al, 2017;Chalek et al, 2021;Wang et al, 2021). Recently, plane-wave EFG tensor predictions involving 14 N, 17 O, and 35 Cl nuclei were used to obtain optimized damping parameters for crystal geometry refinement using Grimme's DFT-D2 scheme (Holmes and Schurko, 2018).…”

Section: Modeling Disorder In the 4-nitrobenzaldehyde Crystal Structurementioning

confidence: 99%

“…SSNMR investigations are often coupled with X-ray diffraction and first-principals calculations to form the interdisciplinary field of NMR crystallography. The success of NMR crystallography has been greatly facilitated by the availability of accurate computational methods for predicting NMR parameters which typically employ density functional theory (DFT) (Gervais et al, 2005;Wu, 2008;Kong et al, 2013;Yang et al, 2016;Kong et al, 2017;Soss et al, 2017;Holmes and Schurko, 2018;Yamada et al, 2020;Chalek et al, 2021;Wang et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

2021

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Modern approaches for calculating electric field gradient (EFF) tensors in molecular solids rely upon plane-wave calculations employing periodic boundary conditions (PBC). In practice, models employing PBCs are limited to generalized gradient approximation (GGA) density functionals. Hybrid density functionals applied in the context of gauge-including atomic orbital (GIAO) calculations have been shown to substantially improve the accuracy of predicted NMR parameters. Here we propose an efficient method that effectively combines the benefits of both periodic calculations and single-molecule techniques for predicting electric field gradient tensors in molecular solids. Periodic calculations using plane-wave basis sets were used to model the crystalline environment. We then introduce a molecular correction to the periodic result obtained from a single-molecule calculation performed with a hybrid density functional. Single-molecule calculations performed using hybrid density functionals were found to significantly improve the agreement of predicted 17O quadrupolar coupling constants (Cq) with experiment. We demonstrate a 31% reduction in the RMS error for the predicted 17O Cq values relative to standard plane-wave methods using a carefully constructed test set comprised of 22 oxygen-containing molecular crystals. We show comparable improvements in accuracy using five different hybrid density functionals and find predicted Cq values to be relatively insensitive to the choice of basis set used in the single molecule calculation. Finally, the utility of high-accuracy 17O Cq predictions is demonstrated by examining the disordered 4-Nitrobenzaldehyde crystal structure.

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“…The first example of the large photomechanical expansion of organic molecular crystals was reported by Bardeen et al, who observed an average 8% expansion of 9- tert -butyl-anthracene ester (9TBAE) nanorods . Subsequent studies suggested that the 9TBAE nanorod expansion did not result from the molecular volume change but instead resulted from the rearrangement of molecular contents. , Recent studies have shown that molecular orientation is coherently correlated with photomechanical behavior and photochemical dynamics. , For our ( E )- NAAM hollow microcrystals, the significant molecular geometry and structural changes from parallel stacking monomeric pairs to butterfly-like photodimers satisfy the first prerequisite for expansion (Figure S19). Although there was no direct comparison between the crystal volume of the monomer and the photoreacted dimer, the formation of the highly distorted photodimer suggests that the crystal lattice might have experienced expansion during photodimerization.…”

Section: Results and Discussionmentioning

confidence: 76%

Engineering Photomechanical Molecular Crystals to Achieve Extraordinary Expansion Based on Solid-State [2 + 2] Photocycloaddition

Tong

et al. 2022

J. Am. Chem. Soc.

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Photomechanical molecular crystals are promising candidates for photoactuators and can potentially be implemented as smart materials in various fields. Here, we synthesized a new molecular crystal, (E)-3-(naphthalen-1yl)acrylaldehyde malononitrile ((E)-NAAM), that can undergo a solid-state [2 + 2] photocycloaddition reaction under visible light (≥400 nm) illumination. (E)-NAAM microcrystals containing symmetric twinned sealed cavities were prepared using a surfactant-mediated crystal seeded growth method. When exposed to light, the hollow microcrystals exhibited robust photomechanical motions, including bending and dramatic directional expansion of up to 43.1% elongation of the original crystal length before fragmentation due to the photosalient effect. The sealed cavities inside the microcrystals could store different aqueous dye solutions for approximately one month and release the solutions instantly upon light irradiation. A unique slow−fast−slow crystal elongation kinematic process was observed, suggesting significant molecular rearrangements during the illumination period, leading to an average anisotropic crystal elongation of 37.0% (±3.8%). The significant molecular structure and geometry changes accompanying the photocycloaddition reaction, which propels photochemistry to nearly 100% completion, also facilitate photomechanical crystal expansion. Our results provide a possible way to rationally design molecular structures and engineer crystal morphologies to promote more interesting photomechanical behaviors.

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Bridging photochemistry and photomechanics with NMR crystallography: the molecular basis for the macroscopic expansion of an anthracene ester nanorod

Abstract: Crystals composed of photoreactive molecules represent a new class of photomechanical materials with the potential to generate large forces on fast timescales. An example is the photodimerization of 9-tertbutyl-anthracene ester (9TBAE)...

Cited by 27 publications

References 95 publications

Correlating Reaction Dynamics and Size Change during the Photomechanical Transformation of 9‐Methylanthracene Single Crystals

Correlating Reaction Dynamics and Size Change during the Photomechanical Transformation of 9‐Methylanthracene Single Crystals

Fast and Accurate Electric Field Gradient Calculations in Molecular Solids With Density Functional Theory

Engineering Photomechanical Molecular Crystals to Achieve Extraordinary Expansion Based on Solid-State [2 + 2] Photocycloaddition

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