Organic Crystals Research Articles

Exceptionally High-glum Circularly Polarized Lasers Empowered by Strong 2D-Chiroptical Response in a Host-Guest Supramolecular Microcrystal.

Circularly polarized (CP) lasers hold tremendous potential for advancing spin information communication and display technologies. Organic materials are emerging candidates for high-performance CP lasers because of their abundant chiral structures and excellent gain characteristics. However, their dissymmetry factor (glum) in CP emission is typically low due to the weak chiral light matter interactions. Here, we presented an effective approach to significantly amplifying glum by leveraging the intrinsic 2D-chiroptical response of an anisotropic organic supramolecular crystal. The organic complex microcrystal was designed to exhibit large 2D-chiroptical activities through strong coupling interactions between their remarkable linear birefringence (LB) and high degree of fluorescence linear polarization. Such 2D-chiroptical response can be further enhanced by the stimulated emission resulted from an increased degree of linear polarization, yielding a nearly pure CP laser with an exceptionally high glum of up to 1.78. Moreover, exploiting the extreme susceptibility of LB to temperature, we demonstrate a prototype of temperature-controlled chiroptical switches. These findings offer valuable insights for harnessing organic crystals to facilitate the development of high-performance CP lasers and other chiroptical devices.

Unveiling High Electro‐Optic Performance in a Proton–π‐Electron‐Coupled Ferroelectric Crystal

AbstractThe convergence of electronics and photonics is attracting attention for its potential to surpass performance limitations of existing information‐processing devices. In particular, the electro‐optic (EO) effect plays a critical role in high‐speed and low‐power conversion between electrical and optical signals, which is demanded for future communication networks. Here, a novel class of EO material is demonstrated, the organic ferroelectric crystal of croconic acid (CRCA). The recently developed birefringence field‐modulation imaging technique enables high‐throughput evaluation of the EO coefficient for as‐grown bulk crystals, unveiling a figure of merit of >400 for CRCA, which exceeds that of 320 in the conventional EO material LiNbO3 in the visible‐light range. Analyses in conjunction with theoretical calculations clarify that its remarkable EO performance is attributable to deformation of the π‐orbital coupled with the proton displacement. This finding provides a new route for the molecular design of high‐performance EO materials: proton–π‐electron‐coupled ferroelectrics.

Exploring the impact of solvent on growth, morphology and photoluminescence properties of organic electro-optic OH1 single crystal

Exploring the impact of solvent on growth, morphology and photoluminescence properties of organic electro-optic OH1 single crystal

Low-threshold distributed feedback laser based on holographic polymer dispersed liquid crystals through the oriented organic semiconductor films

A specific optimized configuration for low threshold organic semiconductor laser based on a holographic polymer dispersed liquid crystal (HPDLC) transmission grating was demonstrated. Here the organic semiconductor films and phase separated liquid crystal (LC) molecules were oriented along the direction of the HPDLC grating grooves. The influence of the organic semiconductor chain orientation and the excitation polarization on the optical properties of the materials has been investigated. Especially, when polymer chain orientation, LC molecules and pump light polarization are consistent with the direction of the grating grooves, the performance of the outgoing laser is greatly improved. Up to 9.78% conversion efficiency with a threshold lower to 0.12 μJ/pulse can be obtained, indicating their potential for high-performance organic optoelectronics.

Evaluation of the optical, photoluminescence, and thermal characteristics of Barium thiourea chloride (BTCL), a metal–organic crystal for photonic applications

The development of crystal fabrication and characterization approaches makes it possible to study novel materials with enhanced linear and nonlinear optical properties. The solution growth method was adopted in the present investigation to create Barium thiourea chloride (BTCL), a metal–organic single crystal. Structural, optical, and thermal characteristics of the BTCL crystals were evaluated by XRD analysis, Fourier transform infrared spectroscopy, UV–Vis spectrometry, photoluminescence, SHG, and thermal analyses. The XRD method was applied to investigate the structural characteristics of the BTCL, which is related to the monoclinic structure. The FT-IR spectral investigation was conducted to observe the vibrational modes in BTCL. The optical measurements showed the transmittance in the near-UV and visible spectrums. Optical characteristics include bandgap, refractive index, extinction coefficient, optical, and electrical conductivities, and dielectric constants were obtained. The PL curve showed two notable emission peaks at 482.5[Formula: see text]nm and 491[Formula: see text]nm. The ability to generate second harmonics was investigated using the Kurtz and Perry method, and the SHG was more than 1.79 times the KDP sample. The thermal behavior of the BTCL was evaluated by TGA/DTA measurements. The Coats–Redfern relation was used to estimate the activation energy of the thermal system and the value was determined to be 9.48[Formula: see text]KJ/mol. The findings indicate that the BTCL crystals possess excellent optical transparency, higher SHG potency, and good thermal stability, which are suitable for use in photonic structures.

The effect of silicon dioxide on the structural, thermal and transport properties of an organic ionic plastic crystal (n-C4H9)4NBF4

Composite solid electrolytes based on an organic ionic plastic crystal (n-C4H9)4NBF4 with highly dispersed SiO2 with specific surface area of Ss = 324±10 m2/g have been studied for the first time. By methods of X-ray diffraction and differential scanning calorimetry, it was found that the introduction of SiO2 leads to amorphization of the salt. An unusual size effect was observed in the composites: the temperature of the polymorphic transition of the salt shifted from 67 °C to 60 °C, while the melting point did not change. The 0.15(n-C4H9)4NBF4–0.85SiO2 composite was found to possess the highest electrical conductivity (σ = 2∙10–5 S/cm at 150 °C), which is 1.5 orders of magnitude higher than that of the initial salt. Modelling of the concentration dependences of the electrical conductivity of composites using the mixing equation showed that the reason for the increase in electrical conductivity is the formation of an amorphous layer of salt, the electrical conductivity of which is 3 orders of magnitude higher than that of the crystalline phase (n-C4H9)4NBF4. The obtained results can be used for the design of high-performance composites based on organic ionic plastic crystals for application in electrochemical devices.

Synthesis of Chlorophylls-Doped Guanine Crystals with High Reflection and Depolarization for Green Camouflage Coating.

Hyperspectral imaging technology can record the spatial and spectral information of the targets and significantly enhance the levels of military reconnaissance and target detection. It has scientific importance to mimic "homochromatic and homospectral" camouflage materials that have hyperspectral similarity with the green vegetation, one of the most common natural backgrounds. It is a big challenge to exquisitely simulate the spectral of green vegetation in visible and near-infrared windows because of the slight differences between the artificial green dyes and vegetation, the instability of chlorophylls, and the easy loss of hydroxide bands due to the loss of water from the camouflage materials. Herein, a novel kind of biomimetic material of green vegetation was designed through the incorporation of chlorophylls into the crystal lattices of single-crystalline anhydrous guanine microplates for the first time. The synthesized chlorophylls-doped anhydrous guanine crystals exhibit high reflectance intensity and depolarization effect, thus can be applied as biomimetic camouflage materials that mimic green vegetation with high reflectivity and low polarization in the visible and near-infrared regions. The factors influencing the formation of dye-doped organic crystals under mild conditions were thoroughly investigated and the characterizations using electron microscopies and fluorescence confocal laser scanning microscopy clearly confirm the occlusion of chlorophylls into the crystal lattices of guanine crystals. The thermal stability experiments clearly indicate that the chlorophylls-doped guanine crystals possess long-term stability at high temperature. This study provides a new strategy for the synthesis of multifunctional materials comprised of organic crystals.

Pyroelectric Organic Crystal of a Bisbiphenylurea with Chiral Side Chains Polarizable under Low Electric Fields Exhibiting a Nonvolatile Polarization Memory even after the Melting–Recrystallization Process

Pyroelectric Organic Crystal of a Bisbiphenylurea with Chiral Side Chains Polarizable under Low Electric Fields Exhibiting a Nonvolatile Polarization Memory even after the Melting–Recrystallization Process

Size Reduction to Enhance Crystal-to-Liquid Phase Transition Induced by E-to-Z Photoisomerization Based on Molecular Crystals of Phenylbutadiene Ester.

Harnessing the photoinduced phase transitions in organic crystals, especially the changes in shape and structure across various dimensions, offers a fascinating avenue for exact spatiotemporal control, which is crucial for developing future smart devices. In our study, we report a new photoactive molecular crystal made from (E)-2-(3-phenyl-allylidene)malonate ((E)-PADM). When exposed to ultraviolet (UV) light at 365 nm, this compound experiences an E-to-Z photoisomerization in liquid solution and a crystal-to-liquid phase transition in solid crystals. Remarkably, nanoscopic crystalline rods boost their melting rate and degree compared to bulk crystals, indicating that miniaturization enhances the photoinduced melting effect. Our results demonstrate a simple approach to rapidly drive molecular crystals into liquids via photochemical reactions and phase transitions.

Exciton Transport in the Nonfullerene Acceptor O-IDTBR from Nonadiabatic Molecular Dynamics.

Theory, computation, and experiment have given strong evidence that charge carriers in organic molecular crystals form partially delocalized quantum objects that diffuse very efficiently via a mechanism termed transient delocalization. It is currently unclear how prevalent this mechanism is for exciton transport. Here we carry out simulation of singlet Frenkel excitons (FE) in a molecular organic semiconductor that belongs to the class of nonfullerene acceptors, O-IDTBR, using the recently introduced FE surface hopping nonadiabatic molecular dynamics method. We find that FE are, on average, localized on a single molecule in the crystal due to sizable reorganization energy and moderate excitonic couplings. Yet, our simulations suggest that the diffusion mechanism is more complex than simple local hopping; in addition to hopping, we observe frequent transient delocalization events where the exciton wave function expands over 10 or more molecules for a short period of time in response to thermal excitations within the excitonic band, followed by de-excitation and contraction onto a single molecule. The transient delocalization events lead to an increase in the diffusion constant by a factor of 3-4, depending on the crystallographic direction as compared to the situation where only local hopping events are considered. Intriguingly, O-IDTBR appears to be a moderately anisotropic 3D "conductor" for excitons but a highly anisotropic 2D conductor for electrons. Taken together with previous simulation results, two trends seem to emerge for molecular organic crystals: excitons tend to be more localized and slower than charge carriers due to higher internal reorganization energy, while exciton transport tends to be more isotropic than charge transport due to the weaker distance dependence of excitonic versus electronic coupling.

Tension Induced Photoluminescence Enhancement in an Organic Single Crystal.

Organic single crystals possess distinct advantages due to their highly ordered molecular structures, resulting in improved stability, enhanced carrier mobility, and superior optical characteristics. However, their mechanical rigidity and brittleness impede the applications in flexible and wearable optoelectronic devices. Here, photoluminescence (PL) emission from 2,6-diphenylanthracene (DPA) single crystals is studied under tensile strain, which shows PL enhancement by more than two times with a strain of ≈1.42%. Such a tension induced PL enhancement is reversible, exhibiting no clear optical degradations during 100 cycles of bending and recovery processes. Theoretical calculations reveal that the deformation of molecular structure under strain induces a decrease of the dihedral between anthracene and benzene moieties in DPA molecules. Further, the increased molecular conjugation enhances the molecular oscillator strength, leading to the brightened PL emission. Meanwhile, with the decreased dihedral, the molecular vibrations in DPA crystals are suppressed, which can reduce the non-radiative decay rate. In contrast, no tension induced PL enhancement is observed in polycrystalline DPA thin films as the strain can be released via the grain boundaries. This study highlights the superior optical performance of DPA single crystals under strain field, which will provide new possibilities for DPA-based flexible devices.

Organic-Inorganic Rubrene/WS2 Heterostructure for Broadband Detection and Polarization Imaging.

Organic single crystals exhibit improved carrier mobility, longer exciton diffusion length, anisotropic charge transport, and unique linear dichroism, while its high exciton binding energy seriously limits the free-carrier generation and photoelectric conversion efficiency. Layered van der Waals heterostructures, which integrate organic crystals with high mobility two-dimensional (2D) inorganic semiconductors, are promising for promoting exciton dissociation and boosting sensitivity by utilizing the interfacial potential and photogating effect. In this work, organic single-crystal rubrene is integrated with a few-layer WS2 to design the high-performance photodetector. The device exhibits an excellent responsivity of 1000 A W-1, and a fast speed of 180 μs, which is far superior to the individual WS2 device. Equally importantly, this device provides excellent polarization detection performance by virtue of the anisotropic properties of rubrene, and the dichroic ratios are 1.56, 1.5, and 1.7 for 375, 405, and 658 nm irradiation, respectively. Finally, several high-resolution single-pixel broadband polarization imaging was demonstrated. Our work shows that organic-inorganic heterostructure is an essential candidate for improving optoelectronics performance and has potential for polarization imaging.

Vacuum deposition of χ(2) nonlinear organic single crystal films on silicon

Integrating second order nonlinear (χ(2)) optical materials on chip is an ongoing challenge for Si photonics. Noncentrosymmetric molecular crystals have the potential to deliver high χ(2) nonlinearity with good thermal stability, but so far have been limited to growth from solution or the melt, which are both difficult to control and scale up in manufacturing. Here, we show that large (>100 μm) single crystal domains of the nonlinear molecule 2-[3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene] malononitrile (OH1) can be grown monolithically on either glass or Si via vacuum evaporation, followed by a short thermal annealing step. The crystallites are tens of nanometer thick and exhibit strong second harmonic generation with their primary χ(2) tensor component lying predominantly in plane. Remarkably, we find that a single domain can grow uninterrupted through nearby channels etched on a Si wafer, which may provide a path to integrate OH1 on Si or Si3N4 waveguides for a broad range of χ(2)-based photonic integrated circuit functionality.

Efficient all-electron hybrid density functionals for atomistic simulations beyond 10 000 atoms.

Hybrid density functional approximations (DFAs) offer compelling accuracy for abinitio electronic-structure simulations of molecules, nanosystems, and bulk materials, addressing some deficiencies of computationally cheaper, frequently used semilocal DFAs. However, the computational bottleneck of hybrid DFAs is the evaluation of the non-local exact exchange contribution, which is the limiting factor for the application of the method for large-scale simulations. In this work, we present a drastically optimized resolution-of-identity-based real-space implementation of the exact exchange evaluation for both non-periodic and periodic boundary conditions in the all-electron code FHI-aims, targeting high-performance central processing unit (CPU) compute clusters. The introduction of several new refined message passing interface (MPI) parallelization layers and shared memory arrays according to the MPI-3 standard were the key components of the optimization. We demonstrate significant improvements of memory and performance efficiency, scalability, and workload distribution, extending the reach of hybrid DFAs to simulation sizes beyond ten thousand atoms. In addition, we also compare the runtime performance of the PBE, HSE06, and PBE0 functionals. As a necessary byproduct of this work, other code parts in FHI-aims have been optimized as well, e.g., the computation of the Hartree potential and the evaluation of the force and stress components. We benchmark the performance and scaling of the hybrid DFA-based simulations for a broad range of chemical systems, including hybrid organic-inorganic perovskites, organic crystals, and ice crystals with up to 30 576 atoms (101 920 electrons described by 244 608 basis functions).

Crystal Engineering-Driven Sunlight Responsiveness and Flexible Waveguide Transmission.

Here, a barbituric acid derivative containing pyrene rings (DPPT) was successfully synthesized, and two types of crystals were prepared by using crystal engineering methods. Orange sheet-like crystals (DPPT-O, observed in visible light), prepared in a DCM/CH3OH solution, exhibited brittleness and weak fluorescence emission, along with sunlight-induced bending and fracturing. Red needle-like crystals (DPPT-R, also observed in visible light), synthesized in a DCM/CH3CN solution, demonstrated elastic properties, strong fluorescence emission, and excellent optical waveguide performance (with an optical loss coefficient of 0.23-0.30 dB mm-1). Single-crystal data analysis revealed that the stacking arrangement of molecules critically influenced the elasticity of the crystals, while the reaction cavity size regulated the photomechanical properties of the crystals. This study achieved effective control over sunlight responsiveness and flexible optical waveguide transmission for the first time, providing innovative insights for the application of homogeneous organic polycrystalline molecular crystals in this field.

Understanding Nonlinear Optical Phenomena in N-Pyrimidinyl Stilbazolium Crystals via a Self-Consistent Electrostatic Embedding - DFT Approach.

Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been used to investigate the nonlinear optical (NLO) properties of phenolic N-pyrimidinyl stilbazolium cationic chromophore in its corresponding noncentrosymmetric crystals. Such a cationic chromophore, the OPR (4-(4-hydroxystyryl)-1-(pyrimidin-2-yl)pyridinium), consists of a strong electron donor, the 4-hydroxyphenyl group, and a strong electron acceptor, the N-pyrimidinylpyridinium group based on two electron-withdrawing groups. The in-crystal NLO properties were determined by applying a supermolecule approach in combination with an iterative electrostatic scheme, in which the surrounding molecules of a unit cell are represented by point charges. With CAM-B3LYP, our absolute estimates for the largest diagonal component of the second-order nonlinear susceptibility tensor of OPR-based crystals range from 64.00 to 80.34 pm/V in the static regime and from 162.09 to 175.52 pm/V at 1907 nm. These values are significant when compared to those of benchmark stilbazolium-based crystals. Furthermore, the third-order susceptibility, which is related to the nonlinear optical process of the intensity-dependent refractive index, is also significant compared to the results for other organic crystals, such as chalcone derivatives. With TD-CAM-B3LYP, the two-state model effectively explains the similarity in the first hyperpolarizability values in the crystalline phase. This similarity arises from the combination of the oscillator strength and the charge transfer of the crucial transition. Therefore, phenolic organic salt crystals show great promise for various nonlinear optical applications.

Crystal structures of four thio-glycosides involving carbamimido-thio-ate groups.

The compounds 2',3',4',6'-tetra-O-acetyl-β-d-gluco-pyranosyl N'-cyano-N-phenyl-carbamimido-thio-ate (C22H25N3O9S, 5a), 2',3',4',6'-tetra-O-acetyl-β-d-galacto-pyranosyl N'-cyano-N-phenyl-carbamimido-thio-ate, (C22H25N3O9S, 5b), 2',3',4',6'-tetra-O-acetyl-β-d-galacto-pyranosyl N'-cyano-N-methyl-carbamimido-thio-ate (C17H23N3O9S, 5c), and 2',3',4',6'-tetra-O-acetyl-β-d-galacto-pyranosyl N'-cyano-N-p-tolyl-carbamimido-thio-ate (C23H27N3O9S, 5d) all crystallize in P212121 with Z = 4. For all four structures, the configuration across the central (formal) C=N(CN) double bond of the carbamimido-thio-ate group is Z. The torsion angles C5-O1-C1-S (standard sugar numbering) are all close to 180°, confirming the β position of the substituent. Compound 5b involves an intra-molecular hydrogen bond N-H⋯O1; in 5c this contact is the weaker branch of a three-centre inter-action, whereas in 5a and 5d the H⋯O distances are much longer and do not represent significant inter-actions. The C-N bond lengths at the central carbon atom of the carbamimido-thio-ate group are almost equal. All C-O-C=O torsion angles of the acetyl groups correspond to a synperiplanar geometry, but otherwise all four mol-ecules display a high degree of conformational flexibility, with many widely differing torsion angles for equivalent groups. In the crystal packing, 5a, 5c and 5d form layer structures involving the classical hydrogen bond N-H⋯Ncyano and a variety of 'weak' hydrogen bonds C-H⋯O or C-H⋯S. The packing of 5b is almost featureless and involves a large number of borderline 'weak' hydrogen bonds. In an appendix, a potted history of wavelength preferences for structure determination is presented and it is recommended that, even for small organic crystals in non-centrosymmetric space groups, the use of Mo radiation should be considered.

Model of Suppression of Dynamic Conductivity in Solid-State Phases of an Organic Ionic Plastic Crystal

Model of Suppression of Dynamic Conductivity in Solid-State Phases of an Organic Ionic Plastic Crystal

Organic polymorphic crystals with multi-stimuli response: excellent mechanical elasticity, novel two-stage heterotropic photochromism and self-reversible acidichromism

Organic polymorphic crystals with multi-stimuli response: excellent mechanical elasticity, novel two-stage heterotropic photochromism and self-reversible acidichromism

Force Field X: A computational microscope to study genetic variation and organic crystals using theory and experiment.

Force Field X (FFX) is an open-source software package for atomic resolution modeling of genetic variants and organic crystals that leverages advanced potential energy functions and experimental data. FFX currently consists of nine modular packages with novel algorithms that include global optimization via a many-body expansion, acid-base chemistry using polarizable constant-pH molecular dynamics, estimation of free energy differences, generalized Kirkwood implicit solvent models, and many more. Applications of FFX focus on the use and development of a crystal structure prediction pipeline, biomolecular structure refinement against experimental datasets, and estimation of the thermodynamic effects of genetic variants on both proteins and nucleic acids. The use of Parallel Java and OpenMM combines to offer shared memory, message passing, and graphics processing unit parallelization for high performance simulations. Overall, the FFX platform serves as a computational microscope to study systems ranging from organic crystals to solvated biomolecular systems.