Strategies to Diversification of the Mechanical Properties of Organic Crystals.

Structurally ordered soft materials that respond to complementary stimuli are susceptible to control over their spatial and temporal morphostructural configurations by intersectional or combined effects such as gating, feedback, shape-memory, or programming. In the 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 not only elastic but also motile, displaying the rare photosalient effect.

Molecular Twisting Affects the Solid-State Photochemical Reactions of Unsaturated Ketones and the Photomechanical Effects of Molecular Crystals.

Three groups of chalcone derivatives and their analogues involving halogen atoms (X=F, Cl, Br) have been synthesized. Firstly, the nearly planar acyclic chalcone derivatives were inclined to undergo photo-induced stereospecific [2+2] cycloaddition, which triggered the crystals to exhibit macroscopic motions of bending or cracking. In particular, the single-crystal-to-single-crystal transformation happened upon UV irradiation of the crystals, which was helpful for the understanding photomechanical effects. Cyclic 3,4-dihydronaphthalene-based chalcone analogues possess a more twisted conformation, and they tend to undergo trans-cis isomerization. No photomechanical effect was observed for the crystals of the cyclic chalcone analogues due to the lower isomerization rate. The twist degree of chroman-based molecules was in between of the first two, [2+2] cycloaddition and trans-cis isomerization simultaneously took place in crystals. Photo-induced bending and twisting were observed for the crystals of chroman-based chalcone analogues. Therefore, the differences in molecular dihedral angles in α,ß-unsaturated ketones were responsible for their photochemical characters and in turn to tune the photomechanical effects. In this work, a bridge between the molecular structures and solid-state photochemical reactions triggered photomechanical crystals is built.

Low-Pressure Sensitive Piezochromic Fluorescence Switching of Tetraphenylethylene-Anthraquinone.

Invited for the cover of this issue are Prof. Wenjing Tian and co-workers at Jilin University. The image depicts the highly sensitive piezochromic fluorescence switching of tetraphenylethylene-anthraquinone under low-pressure regimes (∼60 kPa). Read the full text of the article at 10.1002/chem.202301070.

Low-Pressure Sensitive Piezochromic Fluorescence Switching of Tetraphenylethylene-Anthraquinone.

Sensing of low-pressure signals is of great importance for cutting-edge technologies. Organic piezochromic molecules offer a promising library of pressure sensitive materials which can be tailor-designed toward specific requirements. However, very few examples of low-pressure sensitive piezochromic fluorescent molecules have been obtained till date, and the underlying mechanisms are still in its infancy. Herein, we report highly sensitive piezochromic fluorescent switching under low-pressure regimes (∼60 kPa) of tetraphenylethylene-anthraquinone (TPE-AQ) based on the controlled molecular design and polymorphic phase strategy. The influence of both intramolecular conformation effect and variations of intermolecular stacking modes on the piezochromic property of TPE-AQ is investigated. The underlying mechanism of the low-pressure sensitive piezochromic fluorescence switching is demonstrated to be closely related to the loosely packed molecular orientation, as confirmed by X-ray diffraction measurements combined with simulations. This work provides a way to design highly efficient pressure sensors based on organic molecular systems.

Single-crystalline hole-transporting layers for efficient and stable organic light-emitting devices.

Efficient charge-carrier injection and transport in organic light-emitting devices (OLEDs) are essential to simultaneously achieving their high efficiency and long-term stability. However, the charge-transporting layers (CTLs) deposited by various vapor or solution processes are usually in amorphous forms, and their low charge-carrier mobilities, defect-induced high trap densities and inhomogeneous thickness with rough surface morphologies have been obstacles towards high-performance devices. Here, organic single-crystalline (SC) films were employed as the hole-transporting layers (HTLs) instead of the conventional amorphous films to fabricate highly efficient and stable OLEDs. The high-mobility and ultrasmooth morphology of the SC-HTLs facilitate superior interfacial characteristics of both HTL/electrode and HTL/emissive layer interfaces, resulting in a high Haacke's figure of merit (FoM) of the ultrathin top electrode and low series-resistance joule-heat loss ratio of the SC-OLEDs. Moreover, the thick and compact SC-HTL can function as a barrier layer against moisture and oxygen permeation. As a result, the SC-OLEDs show much improved efficiency and stability compared to the OLEDs based on amorphous or polycrystalline HTLs, suggesting a new strategy to developing advanced OLEDs with high efficiency and high stability.

Isomer Discrimination via Defect Engineering in Monolayer MoS2.

The all-surface nature of two-dimensional (2D) materials renders them highly sensitive to environmental changes, enabling the on-demand tailoring of their physical properties. Transition metal dichalcogenides, such as 2H molybdenum disulfide (MoS2), can be used as a sensory material capable of discriminating molecules possessing a similar structure with a high sensitivity. Among them, the identification of isomers represents an unexplored and challenging case. Here, we demonstrate that chemical functionalization of defect-engineered monolayer MoS2 enables isomer discrimination via a field-effect transistor readout. A multiscale characterization comprising X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and electrical measurement corroborated by theoretical calculations revealed that monolayer MoS2 exhibits exceptional sensitivity to the differences in the dipolar nature of molecules arising from their chemical structure such as the one in difluorobenzenethiol isomers, allowing their precise recognition. Our findings underscore the potential of 2D materials for molecular discrimination purposes, in particular for the identification of complex isomers.

[Early ST resolution after successful primary PCI is related to a favorable outcome in ST elevated AMI patients].

OBJECTIVE: To analyze the relationship between the early ST resolution magnitude and TIMI flow, MACE and the cardiac function in ST elevated AMI (STEMI) patients after successful primary PCI. METHODS: A total of 120 consecutive patients with STEMI underwent primary PCI within 12 hours after the onset of chest pain were enrolled in this study, the ST segment resolution was calculated and the patients were divided into group A (n = 81, Sigma STE resolved > or = 50%) and group B (n = 39, Sigma STE resolved < 50%). TIMI flow after PCI, clinical events up to 30 days post PCI and cardiac function 30 days post PCI were assessed. RESULTS: LVEF was higher in group A than that of group B (58.6% +/- 7.1% vs. 50.5% +/- 7.1%, P < 0.05). There are fewer patients with Killip III and IV in group A than in group B (1.2% vs. 12.8%, P < 0.05). The incidence of in-hospital MACE was also significantly less in group A than in group B (0 vs. 7.7%, P < 0.001). As expected, there were more patients with TIMI 3 flow (95.1% vs. 79.5%, P < 0.05) and fewer TIMI 2 (4.9% vs. 20.5%, P < 0.05) flow post PCI in group A than in group B and all 3 patients with MACE were group B patients with TIMI 2 flow. CONCLUSION: Early ST resolution post PCI represents improved myocardial perfusion and function and is related to a favorable clinical outcome in STEMI patients.