A Flexible Organic Single Crystal with Plastic‐Twisting and Elastic‐Bending Capabilities and Polarization‐Rotation Function

Flexible organic single crystals capable of plastic or elastic deformations have a variety of potential applications. Although the integration of plasticity and elasticity in a crystal is theoretically possible and it may cause rich and complex deformations which are highly demanded for potential applications, the integration is hard to realize in practice. Here, we show that through utilizing different modes of external forces for influencing molecular packing in different crystallographic directions, plastic helical twisting and elastic bending can both be achieved for a crystal, and they can even be realized simultaneously. Detailed crystallographic analyses and contrast experiments disclose the mechanisms behind these two kinds of distinct deformations and their mutual compatibility. Based on the plastically twistable nature of the crystal, a new application field of flexible organic single crystals, namely polarization rotators, is successfully opened up.     

Elastic Organic Crystals Based on Barbituric Derivative: Multi-faceted Bending and Flexible Optical Waveguide

Elastic organic single crystals with light-emitting and multi-faceted bending properties are extremely rare. They have potential application in optical materials and have attracted the extensive attention of researchers. In this paper, we reported a structurally simple barbituric derivative DBDT , which was easily crystallized and gained long needle-like crystals (centimeter-scale) in DCM/CH₃OH (v/v=2/8). Upon applying or removing the mechanical force, both the (100) and (040) faces of the needle-like crystal showed reversible bending behaviour, showing the nature of multi-faceted bending. The average hardness (H) and elastic modulus (E) were 0.28±0.01 GPa and 4.56±0.03 GPa for the (040) plane, respectively. Through the analysis of the single crystal data, it could be seen that the van der waals (C−H⋅⋅⋅π and C−H⋅⋅⋅C), H-bond (C−H⋅⋅⋅O) and π⋅⋅⋅π interactions between molecules were responsible for the generation of the crystal elasticity. Interestingly, elastic crystals exhibited optical waveguide characteristics in straight or bent state. The optical loss coefficients measured at 627 nm were 0.7 dBmm⁻¹ (straight state) and 0.9 dBmm⁻¹ (bent state), while the optical loss coefficient (α) were 1.5 dBmm⁻¹ (straight state) and 1.8 dBmm⁻¹ (bent state) at 567 nm. Notably, the elastic organic molecular crystal based on barbituric derivative could be used as the candidate for flexible optical devices.     

Highly Elastic Organic Crystals for Flexible Optical Waveguides

The study of elastic organic single crystals (EOSCs) has emerged as a cutting‐edge research of crystal engineering. Although a few EOSCs have been reported recently, those suitable for optical/optoelectronic applications have not been realized. Here, we report an elastic crystal of a Schiff base, (E)‐1‐(4‐(dimethylamino)phenyl)iminomethyl‐2‐hydroxyl‐naphthalene. The crystal is highly bendable under external stress and able to regain immediately its original straight shape when the stress is released. It displays bright orange–red emission with a high fluorescence quantum yield of 0.43. Intriguingly, it can serve as a low‐loss optical waveguide even at the highly bent state. Our result highlights the feature and utility of “elasticity” of organic crystals.     

Multi-Stimuli-Induced Mechanical Bending and Reversible Fluorescence Switching in a Single Organic Crystal

Fluorescent single crystals that respond to multiple external stimuli are of great interest in molecular machines, sensors, and displays. The integration of photo- or acid-induced fluorescence enhancement and bending in one organic crystal, however, has not been reported yet. Herein, we report the interesting plastic photomechanical bending and switching on of the fluorescence of an azine crystal in a single-crystal transformation, due to extended π-conjugation and molecular slippage. Moreover, the fluorescent plastic bending driven by multiple volatile acid vapors was firstly observed, and attributed to the synergistic effect of push–pull electronic structure and hydrogen bonding. The single crystal also shows high elasticity under external force. In addition, reversible fluorescence switching can be triggered by grinding and solvent fuming, as well as by the adsorption and desorption of HCl vapor. The integration of plastic, elastic bending and switch-on fluorescence into one single crystal provides a new strategy for next-generation smart materials.     

多孔有机盐单晶的合成及各向异性质子导电性能

以cis,cis-1,3,5-三氨基环己烷·3HBr和均苯四甲酸在室温下通过离子键构筑了具有规整形貌和大尺寸的晶态多孔有机盐CPOS-10, 其具有较好的热稳定性和永久多孔性. 得益于规整形貌及大尺寸单晶, 首次实现了对多孔有机盐单晶各向异性质子导电性能的研究, 并结合晶体结构探索了各向异性质子导电的机理. 结果表明, 水分子浓度对CPOS-10质子电导率的大小具有重要作用, 骨架内水分子浓度高的晶面更易于与极性基团构成氢键网络, 促进质子传导, 利用此网络的质子传导具有更高的质子电导率. 因此, 骨架内水分子的不均匀分布是导致单晶各向异性质子导电的主要原因. 对CPOS-10单晶各向异性质子导电性能的探索可为研究多孔有机盐的质子导电机理提供重要的依据.     

Organic Crystal Growth: Directly from Amorphous Solid Powder to Single Crystals

Preparation of organic crystals mainly depends on solution-deposition, sublimation, and melt-deposition techniques. Solid-state growth methods are generally not suitable for organic crystal growth due to the unprocurable mass transfer. Herein, we report two pyridine-substituted fluorenone compounds with extraordinary crystal-growth capacity, and these compounds can directly and quickly form single crystals from their amorphous solid powder by heating under antisolvent-assistance conditions. The novel experimental phenomenon and crystal growth mechanism were investigated in depth. The results indicate that multiple intermolecular hydrogen-bonding sites and planar aromatic structure (prone to π-π interactions) of these molecules dominate the mass transfer during crystal growth by providing enough energy. This discovery enhances our knowledge of solid-state methods for single-crystal growth.     

Versatile Ferroelastic Deformability in an Organic Single Crystal by Twinning about a Molecular Zone Axis

Ferroelasticity involves the generation of spontaneous strain in a solid by the application of mechanical stress. The phenomenon has been well‐studied in metal alloys but relatively neglected in organic solid‐state chemistry. Herein we present multiple discrete modes of mechanical twinning and a mechanistic analysis of ferroelasticity in 1,4‐diethoxybenzene. Single crystals of the compound can be almost freely deformed, as multiple different twin domains are generated simultaneously. Within each domain, single‐crystal character is preserved. Such extremely versatile, ferroelastic deformability is unprecedented in single crystals of any kind and defies the fragility and anisotropic mechanical behaviour of most organic crystals. The dissipated energy and critical stress associated with twinning deformation in 1,4‐diethoxybenzene suggests that organic solids could be developed for absorbing weak mechanical shocks in such applications as mechanical damping and soft robotics.     

有机单晶电路的研究进展

与传统硅基集成电路相比, 有机集成电路具有成本低、 柔性及易携带等优势. 有机单晶集成电路在有机集成电路的基础上提高了材料的有序度和迁移率, 从而大大提升了电学性能, 具有丰富的研究价值和广泛的应用前景. 本文综合评述了有机单晶电路的研究进展, 重点总结了利用有机单晶制备逻辑门电路的相关工作, 并介绍了将有机单晶用于集成电路上的尝试, 最后分析了有机单晶集成电路研究中面临的挑战并对其未来的发展进行了展望.     

Self-Waveguide Single-Benzene Organic Crystal with Ultralow-Temperature Elasticity as a Potential Flexible Material

With the increasing popularity and burgeoning progress of space technology, the development of ultralow-temperature flexible functional materials is a great challenge. Herein, we report a highly emissive organic crystal combining ultralow-temperature elasticity and self-waveguide properties (when a crystal is excited, it emits light from itself, which travels through the crystal to the other end) based on a simple single-benzene emitter. This crystal displayed excellent elastic bending ability in liquid nitrogen (LN). Preliminary experiments on optical waveguiding in the bent crystal demonstrated that the light generated by the crystal itself could be confined and propagated within the crystal body between 170 and −196 °C. These results not only suggest a guideline for designing functional organic crystals with ultralow-temperature elasticity but also expand the application region of flexible materials to extreme environments, such as space technology.     

Mechanophotonics: Flexible Single‐Crystal Organic Waveguides and Circuits

We present the one‐dimensional optical‐waveguiding crystal dithieno[3,2‐a:2′,3′‐c]phenazine with a high aspect ratio, high mechanical flexibility, and selective self‐absorbance of the blue part of its fluorescence (FL). While macrocrystals exhibit elasticity, microcrystals deposited at a glass surface behave more like plastic crystals due to significant surface adherence, making them suitable for constructing photonic circuits via micromechanical operation with an atomic‐force‐microscopy cantilever tip. The flexible crystalline waveguides display optical‐path‐dependent FL signals at the output termini in both straight and bent configurations, making them appropriate for wavelength‐division multiplexing technologies. A reconfigurable 2×2‐directional coupler fabricated via micromanipulation by combining two arc‐shaped crystals splits the optical signal via evanescent coupling and delivers the signals at two output terminals with different splitting ratios. The presented mechanical micromanipulation technique could also be effectively extended to other flexible crystals.     

Nanoindentation in Crystal Engineering: Quantifying Mechanical Properties of Molecular Crystals

Nanoindentation is a technique for measuring the elastic modulus and hardness of small amounts of materials. This method, which has been used extensively for characterizing metallic and inorganic solids, is now being applied to organic and metal–organic crystals, and has also become relevant to the subject of crystal engineering, which is concerned with the design of molecular solids with desired properties and functions. Through nanoindentation it is possible to correlate molecular‐level properties such as crystal packing, interaction characteristics, and the inherent anisotropy with micro/macroscopic events such as desolvation, domain coexistence, layer migration, polymorphism, and solid‐state reactivity. Recent developments and exciting opportunities in this area are highlighted in this Minireview.     

Room‐Temperature Ferroelectricity in an Organic Cocrystal

Ferroelectric materials exhibit switchable remanent polarization due to reversible symmetry breaking under an applied electric field. Previous research has leveraged temperature‐induced neutral‐ionic transitions in charge‐transfer (CT) cocrystals to access ferroelectrics that operate through displacement of molecules under an applied field. However, displacive ferroelectric behavior is rare in organic CT cocrystals and achieving a Curie temperature (T_C) above ambient has been elusive. Here a cocrystal between acenaphthene and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane is presented that shows switchable remanent polarization at room temperature (T_C=68 °C). Raman spectroscopy, X‐ray diffraction, and solid‐state NMR spectroscopy indicate the ferroelectric behavior is facilitated by acenaphthene (AN) rotation, deviating from conventional design strategies for CT ferroelectrics. These findings highlight the relevance of non‐CT interactions in the design of displacive ferroelectric cocrystals.     

巧用泡沫塑料球自制晶体模型

晶体结构具有重要的教学价值和功能,由于内容较抽象,学生学习起来较为吃力。采用价格低廉的泡沫塑料球与毛绒条扭扭棒为材料,由学生自制晶体模型,安全方便、简单易行,能够有效加深学生对晶体结构的理解,提升学生的学习兴趣。另外,利用泡沫塑料球与毛绒条扭扭棒还可制作许多其他化学教学常用模型,可用度高、推广性强。     

Volatile Organic Compound Sensing by Quartz Crystal Microbalances Coated with Nanostructured Macromolecular Metal Complexes

We report the construction of a molecular recognition layer composed of polyelectrolyte brushes and metal complexes on the surface of a quartz crystal microbalance (QCM) and the sensing abilities for various volatile organic compounds (VOCs). Atom‐transfer radical polymerization of 2‐(dimethylamino)ethyl acrylate from an initiator‐terminated self‐assembled monolayer yielded polyelectrolyte brushes on the surface of a weight‐detectable quartz crystal microbalance. One end of a poly[(2‐dimethylamino)ethyl methacrylate] brush was covalently attached onto the surface of a sensor. We found that metallophthalocyanines with four bulky pentaphenylbenzene substituents could adsorb volatile organic compounds selectively into their cavities. Macromolecular metal complexes were prepared by immersing polymer‐brush‐modified QCMs into an aqueous solution of sterically protected cobalt phthalocyanine. Anionic cobalt phthalocyanine was trapped in the polymer brushes and acted as a molecular receptor for the sensing of VOC molecules.     

Hexagonite: A Hypothetical Organic Zeolite

Elaborating the discrete hydrocarbon molecule bicyclo[2.2.2]-2,5,7-octatriene in three-dimensions, a unique, hypothetical allotrope of carbon is produced. Such a structure possesses a principal 6-fold axis; along this axis are hexagonal, organic tunnels with about a 5.70 Å outside tunnel diameter across opposite vertices, and an actual, inside diameter of 4.16 Å when taking into account the covalent radius of tetrahedral carbon. Across opposite edges, the outside hexagonal tunnel diameter is 4.94 Å, and the inside tunnel diameter is 3.61 Å. These tunnels are lined alternately with hexagonally disposed ethane-like functions and hexagonally disposed ethene-like functions that stack along the tunnel axis. The lattice lies in space group P6/mmm, and it has the Schläfli symbol given by (6, 3^2/5), it is therefore topologically related to the graphite–diamond hybrids. Because of the hexagonal symmetry of the unit cell, and also due to the fact that its polygonality is six, the structure has been given the name hexagonite. There are 10 carbon atoms in the unit of pattern, and the density is 2.50 g/cm³; bordered by the densities of graphite at 2.27 g/cm³ and diamond at 3.56  g/cm³. Its large organic channels, lined with π organic functions, may make it particularly useful as an organic zeolite material, or alternatively as a host lattice for ionic conduction. The electronic band structure of the empty, hexagonal host lattice is described.     

Organic Crystal Rings Formed in Template Polymer Pores by Evaporation of Solvent

Summary: The fabrication of organic crystals into useful forms might play an important role in future electronics technology. A method for fabricating organic crystal rings has been developed. The self‐assembly of six‐armed poly(methyl methacrylate) with a triphenylene core leads to the formation of pores homogeneously distributed in the polymer film. Because the solubility of this polymer in tetrahydrofuran (THF) is lower than that of 2,3,6,7,10,11‐hexamethacrylate triphenylene (HMTP), the holes initially formed and distributed in the polymer film are filled with a THF solution of HMTP. Crystallization nucleation occurs at the edge of holes and HMPT crystals grow at the contact line to form organic crystal rings.

Schematic illustration of crystal‐ring formation.     

以二亚乙基三胺为模板的链状结构硫酸钬配合物的合成、晶体结构及性质

通过溶剂热技术合成了一种以二亚乙基三胺(dien)为模板的链状结构硫酸钬(H₃dien)[Ho(SO₄)₃(H₂O)₂] (1),并通过X射线分析、红外光谱、元素分析和粉末衍射进行了表征。X射线晶体结构分析,化合物1结晶于单斜晶系,P2₁/c空间群,a=0.660 20(13) nm,b=1.476 7(3) nm,c=1.655 6(3)nm,β=93.313(2)°,V=1.611 4(5) nm³,Z=4。化合物1是由HoO₈多面体和SO₄四面体为建筑单元构建成新颖的单一链状结构。在a轴方向上,配位水分子通过氢键连接相邻的链形成三维超分子结构。有机胺分子镶嵌于链间,在合成化合物1合成过程中,pH值(pH=1.5)起了关键作用。     

铌酸锂单晶光纤包层研究

通过镁离子内扩散铌酸锂单晶光纤，以改变晶纤表层的折射率，首次在国内实现了沿不同轴向生长、不同掺杂的铌酸锂单晶光纤的芯－包层波导结构。通过匹配扩散温度、扩散时间、ＭｇＯ膜厚等扩散参数及选择合适的晶纤直径，实现了晶纤具有阶跃和抛物折射率分布的包层，并对包层晶纤的模式特性进行了观察，得到低次模传输。     

The Impact of Interlayer Electronic Coupling on Charge Transport in Organic Semiconductors: A Case Study on Titanylphthalocyanine Single Crystals

Traditionally, it is believed that three‐dimensional transport networks are preferable to those of lower dimensions. We demonstrate that inter‐layer electronic couplings may result in a drastic decrease of charge mobilities by utilizing field‐effect transistors (FET) based on two phases of titanyl phthalocyanine (TiOPc) crystals. The α‐phase crystals with electronic couplings along two dimensions show a maximum mobility up to 26.8 cm² V^?1 s^?1. In sharp contrast, the β‐phase crystals with extra significant inter‐layer electronic couplings show a maximum mobility of only 0.1 cm² V^?1 s^?1. Theoretical calculations on the bulk crystals and model slabs reveal that the inter‐layer electronic couplings for the β‐phase devices will diminish remarkably the device charge transport abilities owing to the coupling direction perpendicular to the current direction. This work provides new insights into the impact of the dimensionality and directionality of the packing arrangements on charge transport in organic semiconductors.     

Postsynthetic Improvement of the Physical Properties in a Metal–Organic Framework through a Single Crystal to Single Crystal Transmetallation

A single crystal to single crystal transmetallation process takes place in the three‐dimensional (3D) metal–organic framework (MOF) of formula Mg^II₂{Mg^II₄[Cu^II₂(Me₃mpba)₂]₃}?45 H₂O ( 1 ; Me₃mpba^4?=N,N′‐2,4,6‐trimethyl‐1,3‐phenylenebis(oxamate)). After complete replacement of the Mg^II ions within the coordination network and those hosted in the channels by either Co^II or Ni^II ions, 1 is transmetallated to yield two novel MOFs of formulae Co₂^II{Co^II₄[Cu^II₂(Me₃mpba)₂]₃}?56 H₂O ( 2 ) and Ni₂^II{Ni^II₄[Cu^II₂(Me₃mpba)₂]₃}? 54 H₂O ( 3 ). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties.