Organic Crystals Research Articles

Room-Temperature Phase Transition Material with Switchable Second-Order Nonlinear Optical Properties.

Phase transition materials with switchable second-order nonlinear optical (NLO) properties have attracted extensive attention because of their great application potential in photoelectric switches, sensors, and modulators, while metal-free organics with NLO switchability near room temperature remain scarce. Herein, we report a hydrogen-bonded metal-free organic crystal, 2-methylpropan-2-aminium 2,2-dimethylpropanoate (1), exhibiting a room-temperature phase transition and favorable NLO switchability. Through investigations on its thermal anomalies, dielectric properties, and crystal structures, we uncover that 1 holds a near-room-temperature phase transition at 303 K from noncentrosymmetric point group C2v to centrosymmetric one D2h, which is attributed to the order-disorder transformations of both tert-butylamine cations and dimethylpropionic acid anions. Accompanied by symmetry change during the phase transition, 1 exhibits reversible and repeatable NLO "on-off" switchability with a desirable switching contrast ratio of ca. 19 between high and low NLO states. This discovery demonstrates a metal-free organic crystal with NLO switching behavior near room temperature, serving as a promising candidate in smart and ecofriendly photoelectric functional materials and devices.

Design Rules to Optimize the Intermolecular and Long-Range Packing of Organic Semiconductor Crystals

Design Rules to Optimize the Intermolecular and Long-Range Packing of Organic Semiconductor Crystals

Symmetry Reduction of Molecular Shape of Cationic Chromophores for High‐Performance Terahertz Generators

AbstractThe symmetry reduction of molecular shape of cationic chromophores as a design strategy to develop organic terahertz (THz) generators is used. Electron donating group (EDG) with an asymmetric shape is introduced into two types of cationic styryl‐quinolinium chromophores, leading to the development of several novel non‐centrosymmetric crystals with high macroscopic optical nonlinearity. In contrast, when an EDG with a symmetric shape is introduced, centrosymmetric crystal structure is obtained in all investigated crystals. For THz wave generation, crystals based on asymmetrically shaped EDG exhibit several optimal crystal characteristics, including a plate‐shape morphology, a large size, and an in‐plane polar axis. Furthermore, over the entire range of molecular phonon vibrations, 0.5–4 THz, the steric hindrance group in the asymmetrically shaped EDG has a strong influence on the suppression of THz phonon vibrations, leading to a low THz absorption coefficient. The crystals based on asymmetrically shaped EDG generate an ≈40 times stronger THz electric field than the inorganic ZnTe crystal and very broad THz spectra, extending up to 16 THz. Thus, the symmetry reduction of the molecular shape of cationic chromophores through the introduction of an asymmetrically shaped EDG is an effective design approach for the development of novel organic THz crystals.

Highly efficient in crystallo energy transduction of light to work.

Various mechanical effects have been reported with molecular materials, yet organic crystals capable of multiple dynamic effects are rare, and at present, their performance is worse than some of the common actuators. Here, we report a confluence of different mechanical effects across three polymorphs of an organic crystal that can efficiently convert light into work. Upon photodimerization, acicular crystals of polymorph I display output work densities of about 0.06-3.94 kJ m-3, comparable to ceramic piezoelectric actuators. Prismatic crystals of the same form exhibit very high work densities of about 1.5-28.5 kJ m-3, values that are comparable to thermal actuators. Moreover, while crystals of polymorph II roll under the same conditions, crystals of polymorph III are not photochemically reactive; however, they are mechanically flexible. The results demonstrate that multiple and possibly combined mechanical effects can be anticipated even for a simple organic crystal.

Shape-Dependent Optical Waveguides and Low-Threshold Lasers from Polymorphic Two-Dimensional Organic Single Crystals.

Organic single crystals (OSCs) with uniform morphologies and highly ordered molecular aggregations are promising for high-performance optoelectronic devices, such as organic solid-state lasers (OSSLs), organic light-emitting transistors (OLETs), and organic light-emitting diodes (OLEDs). However, manipulating OSC morphologies and aggregation is challenging. In this study, we synthesized two-dimensional (2D) OSCs of 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) in hexagonal and parallelogram microplate (H-MP and P-MP) forms. Both types exhibit H-aggregation in the 2D plate plane but with different molecular transition dipole moment (TDM) orientations. This leads to different photon coupling modes with H-MP and P-MP microcavities. H-MPs enable isotropic 2D-waveguiding, forming whispering gallery mode (WGM) resonators, while P-MPs create unidirectional waveguiding, forming Fabry-Pérot mode (FP) resonators. These resonators can generate low-threshold laser emissions at 467 and 473 nm, respectively, and exhibit superior lasing stability with a half-life exceeding 2 h. Our BSBCz microplate OSCs are attractive candidates to combine controlled organic microcavities with photon transporting for realizing future integrated optoelectronic devices.

Molecular electrostatic potential (MEP), thermodynamic properties and spectral analysis of methyl orange doped L–lysine sulfate (MLLS) semi organic crystals

AbstractSemi organic compounds enable several structural and bonding methods for the molecular engineering of novel materials. The optical analysis, methyl orange doped L‐lysine sulfate (MLLS) is an innovative NLO material enabling the rate of frequency up change for stronger systems with lasers in the UV range with clear absorption. With this experimental studies the theoretical studies of the L‐lysine sulfate and its molecules were studied using Gaussian09w software. X‐ray analysis, UV, FTIR, NMR, Mulliken Charges, HOMO‐LUMO, MEP and some related thermodynamic properties were studied. The chosen nucleophilic site is symbolized by the color red, the more popular electrophilic site has been highlighted during MEP mapping. Spectroscopical and thermodynamical properties related to functional behavior of molecules were also discussed with obtained results.

Synthesis and growth of organic 2-ethylimidazolium hydrogen diglycolate single crystal for nonlinear optical applications

A single crystal of 2-Ethylimidazolium hydrogen diglycolate (DAEI) has been grown by slow evaporation solution (SEST) technique at 35 °C. The DAEI crystal belongs to a monoclinic crystal system with a P21/c space group. The Hirshfeld surface analysis determined the grown crystal has the highest intermolecular contribution for O..H interaction. The phase purity and various planes (hkl) of the DAEI crystal system were determined by powder X-ray diffraction analysis (PXRD). The functional groups and their different vibrations of DAEI crystal were identified by Fourier transform infrared analysis. The band gap energy value of the DAEI crystal is found to be 5.32 eV. Photoluminescence measurement reveals that the DAEI crystal has green emission. The material shows major weight losses of around 82.45 % in the temperature between 140 °C and 300 °C. The dielectric analyses were carried out for different frequencies (1Hz–1MHz) and different temperatures. The third-order nonlinear optical properties such as refractive index (n2), absorption coefficient (β) and susceptibility (χ(3)) were determined using the Z-scan technique using a He–Ne laser (λ = 632.8 nm).

Molecularly Thin 2D Organic Single Crystals: A New Platform for High-Performance Polarization-Sensitive Phototransistors.

The inherent linear dichroism (LD), high absorption, and solution processability of organic semiconductors hold immense potential to revolutionize polarized light detection. However, the disordered molecular packing inherent to polycrystalline thin films obscures their intrinsic diattenuation, resulting in diminished polarization sensitivity. In this study, we develop filter-free organic polarization-sensitive phototransistors (PSPs) with both a high linear dichroic ratio (LDR) and exceptional photosensitivity utilizing molecularly thin dithieno[3,2-b:2',3'-d]thiophene derivatives (DTT-8) two-dimensional molecular crystals (2DMCs) as the active layer. The orderly molecular packing in 2DMCs amplifies the inherent LD, and their molecular-scale thickness enables complete channel depletion, significantly reducing the dark current. As a result, PSPs with an impressive LDR of 3.15 and a photosensitivity reaching 3.02 × 106 are obtained. These findings present a practical demonstration of using the polarization angle as an encryption key in optical communication, showcasing the potential of 2DMCs as a viable and promising category of semiconductors for filter-free, polarization-sensitive photodetectors.

Orthogonal printing of uniform nanocomposite monolayer and oriented organic semiconductor crystals for high-performance nano-crystal floating gate memory

Inkjet printing is of great interest in the preparation of optoelectronic and microelectronic devices due to its low cost, low process temperature, versatile material compatibility, and ability to precisely manufacture multi-layer devices on demand. However, interlayer solvent erosion is a typical problem that limits the printing of organic semiconductor devices with multi-layer structures. In this study, we proposed a solution to address this erosion problem by designing polystyrene-block-poly(4-vinyl pyridine)-grafted Au nanoparticles (Au@PS-b-P4VP NPs). With a colloidal ink containing the Au@PS-b-P4VP NPs, we obtained a uniform monolayer of Au nano-crystal floating gates (NCFGs) embedded in the PS-b-P4VP tunneling dielectric (TD) layer using direct-ink-writing (DIW). Significantly, PS-b-P4VP has high erosion resistance against the semiconductor ink solvent, which enables multi-layer printing. An active layer of semiconductor crystals with high crystallinity and well-orientation was obtained by DIW. Moreover, we developed a strategy to improve the quality of the TD/semiconductor interface by introducing a polystyrene intermediate layer. We show that the NCFG memory devices exhibit a low threshold voltage (<3 V), large memory window (66 V), stable endurance (>100 cycles), and long-term retention (>10 years). This study provides universal guidance for printing functional coatings and multi-layer devices.

Unconventional organic low-dimensional crystals: diversity and potential applications

Unconventional organic low-dimensional crystals: diversity and potential applications

Gas Release as an Efficient Strategy to Tune Mechanical Properties and Thermoresponsiveness of Dynamic Molecular Crystals.

Dynamic molecular crystals combining multiple and finely tunable functionalities are attracting and an increasing attention due to their potential applications in a broad range of fields as efficient energy transducers and stimuli-responsive materials. In this context, a multicomponent organic salt, piperazinium trifluoroacetate (PZTFA), endowed with an unusual multidimensional responsive landscape is reported. Crystals of the salt undergo smooth plastic deformation under mechanical stress and thermo-induced jumping. Furthermore, via controlled crystal bending and release of trifluoroacetic acid from the lattice, which is anticipated from the design of the material, both the mechanical response and the thermoresponsive behavior are efficiently tuned while partially preserving the crystallinity of the system. In particular, mechanical deformation hampers guest release and hence the macroscopic jumping effect, while trifluoroacetic acid release stiffens the crystals. These complex adaptive responses establish a new crystal engineering strategy to gain further control over dynamic organic crystals.

Solid‐state room‐temperature phosphorescence activated by the end‐capping strategy of cyano groups

AbstractAvoiding the tedious process of crystal cultivation and directly obtaining organic crystals with desirable phosphorescent performance is of great significance for studying their structure and properties. Herein, a set of benzophenone‐cored phosphors with bright green afterglow are obtained on a large scale through in‐situ generation via an end‐capping strategy to suppress non‐radiative triplet excitons and reinforce the intermolecular interactions. The ordered arrangement of phosphors with alkyl‐cyano groups as regulators is crucial for the enhancement of room‐temperature phosphorescence (RTP) emission, which has been further verified by the attenuated lifetimes in isolated states through the formation of inclusion complexes upon binding with pillar[5]arenes. Moreover, the hierarchical interactions of phosphors, including hydrogen bonding, π‐π stacking interactions, and van der Waals forces, are quantified by crystal structures and theoretical calculation to deeply interpret the origins of RTP emission. With this study, we provide a potential strategy for the direct acquisition of crystalline organic phosphors and modulation of RTP.

Graphene Oxide‐Assisted Molecular Crystal Co‐Assembly for Large‐Scale Freestanding 2D Photoresponse Heterostructures with Synaptic Plasticity

Abstract2D van der Waals heterostructures (2D vdWHs) have been gaining significant attention in neuromorphic electronics. However, the facile synthesis of large‐scale, high‐quality freestanding 2D vdWHs remains challenge, particularly for organic counterparts due to susceptible nucleation behaviors and weak intermolecular interactions. Here, the study reports a graphene oxide (GO)‐assisted molecular crystal co‐assembly method for one‐step growth of centimeter‐scale freestanding heterostructures. This co‐assembly involves the simultaneous assembling of organic and GO precursors at the liquid–liquid interface, where the amphiphilic nature of GO nanosheets facilitates the diffusion of organic molecules and 2D nucleation of organic crystals, and the nanosheets also become enriched to grow a quasi‐solid film for the bilayer formation. Owing to integrated photosensitive and charge‐trapping properties as well as type II band structure, this heterostructure exhibits exceptional photonic synaptic behaviors, with a paired‐pulse facilitation index of 141% and image recognition of 91%.

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.

Realizing the effect of s-block metals on a charge transfer crystal of indol-2-one for enhanced NLO responses with efficient energetic offsets.

Due to their unique photophysical properties, organic charge transfer crystals are becoming promising materials for next-generation optoelectronic devices. This research paper explores the impact of s-block metals on a charge transfer crystal of indol-2-one for enhanced nonlinear optical (NLO) responses with efficient energetic offsets. The study reveals that alkali metals can enhance NLO performance due to their free electrons. The Perdew-Burke-Ernzerhof functional of DFT with dispersion correction (D3) was used, and the λmax values ranged between 596 and 669nm, with the highest value for dichloromethane (DCM). Leveraging the unique properties of metals allowed for the development of nonlinear optical materials with improved performance and versatility. Softness (σ) values provide insight into electron density changes, with higher values indicating a greater tendency for changes and lower values indicating the opposite. The NLO results for the chromophores MMI1-MMI6 show varying linear polarizability (< α0 >) along with their first (β0) and second (γ0) hyperpolarizabilities. Chromophore MMI4 stands out with the highest NLO performance, having two potassium (K) atoms. Its < α0 > , β0, and γ0 values of 4.19, 7.09, and 17.43 (× 10-24 e.s.u), respectively, indicate a significant enhancement in NLO response compared to the other chromophores. The transitions involving (O20)LP → (C3-N5)π* and (O19)LP → (N12-C13)π* exhibit the highest level of stabilization, followed by (O23)π → (C10-C11)π*, while (C6-N12)π → (C6-C7)π* shows the lowest level of stabilization for chromophore MMI4. The present research work is facile in its nature, and it can be helpful for synthetic scientist to design the new materials for uniting crystal properties with metal doping for efficient NLO devices.

Molecularly thin, two-dimensional all-organic perovskites.

Recently, the emergence of all-organic perovskites with three-dimensional (3D) structures has expanded the potential applications of perovskite materials. However, the synthesis and utilization of all-organic perovskites in 2D form remain largely unexplored because the design principle has not been developed. We present the successful synthesis of a metal-free 2D layered perovskite, denoted as the Choi-Loh van der Waals phase (CL-v phase), with the chemical formula A2B2X4, where A represents a larger-sized cation compared to B and X denotes an anion. The CL-v phase exhibits a van der Waals gap enabled by interlayer hydrogen bonding and can be exfoliated or grown as molecularly thin 2D organic crystals. The dielectric constants of the CL-v phase range from 4.8 to 5.5 and we demonstrate their potential as gate dielectrics for thin-film transistors.

A Systematic Study and Biomedical Investigation on O‐Terphenyl Incorporated Copper(II) Chloride Crystal via Slow Evaporation Technique

AbstractCurrent research trends emphasize the need to characterize and analyze the biomedical applications and antibacterial/fungal activity and anticancer studies of O‐terphenyl incorporated copper (II) chloride (OTCC) single crystals by the method of slow evaporation. For this research, a brand‐new inorganic competitive coordination approach is used for crystal formation. As a result, single crystal X‐ray diffraction examination validated the growth of phase in the OTCC crystal. A powder X‐ray diffraction (PXRD) study confirmed the crystalline purity. Fourier transform infrared spectroscopy (FT‐IR) analysis is used to identify the functional groups of organic substances contained in the sample. This sample's optical transparency is assessed using a UV‐Vis‐NIR between 200 and 800 nm in wavelength. In these recent trends, emphasized chemically supported investigation into OTCC crystals and their antibacterial activity and anticancer activity against pathogens are revealed. The outcome of this work will be the effect of metal doping with organic‐based materials, which could be an important reliable weapon in the field of cancer treatment. Many researchers during recent years has done tremendous work exploring and developing drug designs, whereas attention has been drawn to metal‐based organic crystals, metal‐based crystals have the most effect on drug resistance and treat cancer cells. The biological efficacy of this crystal is tested, and it is discovered to have pharmacological qualities such as antibacterial and anticancer capabilities.

Crystal structure, third-order nonlinear optical property relationship, density functional theory, and in silico bio activity of organic non-centrosymmetric crystal (E)-1-(thiophen-2-yl)-3-(p-tolyl)prop-2-en-1-one

Crystal structure, third-order nonlinear optical property relationship, density functional theory, and in silico bio activity of organic non-centrosymmetric crystal (E)-1-(thiophen-2-yl)-3-(p-tolyl)prop-2-en-1-one

Roles of Molecular Volume, Surface Area, Heteroatoms, and Hydrogen Bonds on the Thermal Expansion of Organic Crystals

Roles of Molecular Volume, Surface Area, Heteroatoms, and Hydrogen Bonds on the Thermal Expansion of Organic Crystals

Bending, Twisting, and Propulsion of Photoreactive Crystals by Controlled Gas Release

The rapid release of gas by a chemical reaction to generate momentum is one of the most fundamental ways to elicit motion that could be used to sustain and control the motility of objects. We report that hollow crystals of a three‐dimensional supramolecular metal complex that releases gas by photolysis can propel themselves or other objects and advance in space when suspended in liquid media. In needle‐like regular crystals, the reaction occurs mainly on the surface and results in the formation of cracks that evolve due to internal pressure; the expansion on the cracked surface of the crystal results in bending, twisting, or coiling of the crystal. In hollow crystals, gas accumulates inside their cavity and emanates preferentially from the recess at the crystal terminus, propelling the crystal to undergo directional photomechanical motion through the liquid. The motility of the object which can be controlled externally to perform work delineates the concept of “crystal microbots”, realized by photoreactive organic crystals where prolonged directional motion for actuation or delivery.