Halogen effect in photomechanical molecular crystals

Zhong, Jiangbin; Sun, Jingbo; Ye, Kaiqi; Lu, Ran

doi:10.1039/d3tc03060a

Cited by 9 publications

(8 citation statements)

References 168 publications

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“…During the evaporation process, the thermally evaporated Mg metal diffused into the bulk Li metal, forming Li‐rich solid solutions instead of a distinct layer, as illustrated in Figure 2b(ii), explained by the highly favorable alloying reaction or fast diffusion of Mg into the Li metal. [ 49,56 ] More details are discussed later.…”

Section: Resultsmentioning

confidence: 99%

Rationally Designed Conversion‐Type Lithium Metal Protective Layer for All‐Solid‐State Lithium Metal Batteries

Lim,

Jun,

Song

et al. 2024

Advanced Energy Materials

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A stable interfacial design bridging Li metal and sulfide solid electrolytes is imperative for deploying practical all‐solid‐state Li metal batteries. Despite the extensive exploration of interlayer materials, including inorganic substances, lithiophilic metals, and their composites, a comprehensive understanding of their stability and chemo‐mechanical evolution, particularly those influenced by cell fabrication processes, remains unexplored. Herein, it is meticulously investigate the formation and evolution of LiF, Mg, and conversion‐type multicomponent MgF2 ultrathin interlayers, each fabricated via thermal evaporation deposition. Unexpectedly, LiF and Mg fail to enhance cell performance, with LiF notably susceptible to external pressures during cell fabrication, leading to serious current constriction, while Mg deposition results in the formation of a Li‐rich solid solution. Remarkably, the MgF2 coatings demonstrate substantially superior performance in both Li|Li6PS5Cl|Li symmetric cells (up to 2000 h) and LiNi0.70Co0.15Mn0.15O2|Li6PS5Cl|Li full‐cells (82% capacity retention after 800 cycles) at 30 °C. These results are attributed to the in‐situ formation of LiF and LixMg nanograins through a conversion reaction, which, after repeated cycling, maintains stability and a fixed position at the interface while ensuring uniform interfacial Li+ flux. Supported by comprehensive analyses, these findings highlight the pivotal role of conversion‐type interlayers in mitigating side reactions and preventing Li penetration.

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Section: Resultsmentioning

confidence: 99%

Rationally Designed Conversion‐Type Lithium Metal Protective Layer for All‐Solid‐State Lithium Metal Batteries

Lim,

Jun,

Song

et al. 2024

Advanced Energy Materials

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“…The halogen effect brought about by these halogen atoms improves the molecular π-π stacking, which is an important factor for both crystal flexibility and intermolecular [2+2] cycloaddition. [66] In relation to their [2+2] cycloaddition reactivities, geometrical parameters can be invoked to explain the lack of reactivity of the crystals of E-DiBzE. The reaction cavity of E-DiBzE between two stacked molecules in the crystal was calculated to be 174.782 Å 3 , [67] which is much smaller than the cavities of E-DiBzE-2Cl (281.804 Å 3 ), E-DiBzE-4F (236.577 Å 3 ) and E-DiBzE-4Cl (294.411 Å 3 ).…”

Section: Crystals Of E-dibze-2cl E-dibze-4f and E-dibze-4clmentioning

confidence: 99%

Strategies to Diversification of the Mechanical Properties of Organic Crystals

Dai,

Zhong,

Yang

et al. 2024

Angewandte Chemie

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Structurally ordered soft materials that respond to complementary stimuli are susceptible to control over their spatial and temporal morphostructural configurations via intersectional or combined effects such as gating, feedback, shape‐memory, or programming. In absence of general and robust design and prediction strategies for their mechanical properties, at present, combined chemical and crystal engineering approaches could provide useful guidelines to identify effectors that determine both the magnitude and time of their response. Here, we capitalize on the purported ability of soft intermolecular interactions to instigate mechanical compliance by using halogenation to elicit both mechanical and photochemical activity of organic crystals. Starting from (E)‐1,4‐diphenylbut‐2‐ene‐1,4‐dione, whose crystals are brittle and photoinert, we use double and quadruple halogenation to introduce halogen‐bonded planes that become interfaces for molecular gliding, rendering the material mechanically and photochemically plastic. Fluorination diversifies the mechanical effects further, and crystals of the tetrafluoro derivative are also elastic but also motile, displaying the rare photosalient effect.

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“…Later, in 1964, Schmidt et al developed the concept of “topochemistry” by studying the solid-state photochemical reactions of cinnamic acid derivatives . Since then, the photomechanical effects of organic crystals have been extensively studied. − Many studies have described [2 + 2] cycloaddition reactions involving olefins, − isomerization processes such as trans ( E )– cis ( Z ) isomerization in diarylethenes or azobenzenes, − [4 + 4] photodimerization reactions occurring in anthracene, − and ring opening and closing of diarylethenes, − leading to photoinduced mechanical responses in organic molecular crystals.…”

Section: Introductionmentioning

confidence: 99%

Superelastic and Photomechanical Behavior of Acylhydrazone Derivative Crystals

Peng,

Yang,

Zhao

et al. 2024

Crystal Growth & Design

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The discovery of superelastic organic crystals capable of phototwisting and photobending represents a significant advance in the field of light-responsive materials. This research focused on the synthesis and characterization of crystals derived from trifluoromethyl-substituted acylhydrazone derivatives, known as TBMP. These crystals exhibited remarkable superelasticity when subjected to mechanical forces along their (010) crystallographic plane while showing a tendency to fracture along the (001) plane. Single-crystal analysis revealed that hydrogen bonds, especially C–H···F, C–H···O, and C–H···N interactions, are crucial in providing the crystals with superelastic properties. In addition, reversible E ↔ Z isomerization of TBMP molecules occurred under UV irradiation and heating, resulting in photomechanical (twisting or bending) and thermal recovery behavior of the crystals. Due to their exceptional properties, these crystals possess significant potential for application in robotic arm technology.

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Halogen effect in photomechanical molecular crystals

Abstract: Inspired by the sophistical and intelligent biological systems, various smart actuation triggered by physical or chemical stimuli have been developed. Photomechanical materials that can convert light energy into mechanical work...

Cited by 9 publications

References 168 publications

Rationally Designed Conversion‐Type Lithium Metal Protective Layer for All‐Solid‐State Lithium Metal Batteries

Rationally Designed Conversion‐Type Lithium Metal Protective Layer for All‐Solid‐State Lithium Metal Batteries

Strategies to Diversification of the Mechanical Properties of Organic Crystals

Superelastic and Photomechanical Behavior of Acylhydrazone Derivative Crystals

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