Organic Molecular Crystals Research Articles

Thermoelectric transport in molecular crystals driven by gradients of thermal electronic disorder.

Thermoelectric materials convert a temperature gradient into a voltage. This phenomenon is relatively well understood for inorganic materials but much less so for organic semiconductors (OSs). These materials present a challenge because the strong thermal fluctuations of electronic coupling between the molecules result in partially delocalized charge carriers that cannot be treated with traditional theories for thermoelectricity. Here, we develop a quantum dynamical simulation approach revealing in atomistic detail how the charge carrier wave function moves along a temperature gradient in an organic molecular crystal. We find that the wave function propagates from hot to cold in agreement with the experiment, and we obtain a Seebeck coefficient in good agreement with experimental measurements that are also reported in this work. Detailed analysis reveals that gradients in thermal electronic disorder play an important role in determining the magnitude of the Seebeck coefficient, opening unexplored avenues for the design of OSs with improved Seebeck coefficients.

Latent porosity of planar tris(phenylisoxazolyl)benzene.

Interest in developing separation systems for chemical entities based on crystalline molecules has provided momentum for the fabrication of synthetic porous materials showing selectivity in molecular encapsulation, such as metal-organic frameworks, covalent organic frameworks, hydrogen-bonded organic frameworks, zeolites, and macrocyclic molecular crystals. Among these, macrocyclic molecular crystals have generated renewed interest for use in separation systems. Selective encapsulation relies on the sizes, shapes, and dimensions of the pores present in the macrocyclic cavities; thus, nonmacrocyclic molecular crystals with high selectivity for molecular encapsulation via porosity-without-pore behaviors have not been studied. Here, we report that planar tris(phenylisoxazolyl)benzene forms porous molecular crystals possessing latent pores exhibiting porosity-without-pore behavior. After exposing the crystals to complementary guest molecules, the latent pores encapsulate cis- and trans-decalin while maintaining the structural rigidity responsible for the high selectivity. The encapsulation via porosity without pores is a kinetic process with remarkable selectivity for cis-decalin over trans-decalin with a cis-/trans-ratio of 96:4, which is confirmed by single-crystal X-ray diffraction and powder X-ray diffraction analyses. Hirshfeld surface analysis and fingerprint plots show that the latent intermolecular pores are rigidified by intermolecular dipole‒dipole and π-π stacking interactions, which determines the remarkable selectivity of molecular recognition.

Maneuverability and Processability of Molecular Crystals.

Crystal adaptronics, a burgeoning field at the intersection of materials science and engineering, focuses on harnessing the unique properties of organic molecular crystals to achieve unprecedented levels of maneuverability and processability in various applications. Increasingly, ordered stacks of crystalline materials are being endowed with fascinating mechanical compliance changes in response to external environments. Understanding how these crystals can be manipulated and tailored for specific functions has become paramount in the pursuit of advanced materials with customizable properties. Simultaneously, the processability of organic molecular crystals plays a pivotal role in shaping their utility in real-world applications. From growth methodologies to fabrication techniques, the ability to precisely machine these crystals opens new avenues for engineering materials with enhanced functionality. These processing methods enhance the versatility of organic crystals, allowing their integration into various devices and technologies, and further expanding the potential applications. This review aims to provide a concise overview of the current landscape in the study of dynamic organic molecular crystals, with an emphasis on the interconnected themes of operability and processability.

Polymorphism and Substitutional Effect on the Thermoresponsive and Luminescence Properties of Organic Molecular Crystals

Polymorphism and Substitutional Effect on the Thermoresponsive and Luminescence Properties of Organic Molecular Crystals

Maneuverability and Processability of Molecular Crystals

AbstractCrystal adaptronics, a burgeoning field at the intersection of materials science and engineering, focuses on harnessing the unique properties of organic molecular crystals to achieve unprecedented levels of maneuverability and processability in various applications. Increasingly, ordered stacks of crystalline materials are being endowed with fascinating mechanical compliance changes in response to external environments. Understanding how these crystals can be manipulated and tailored for specific functions has become paramount in the pursuit of advanced materials with customizable properties. Simultaneously, the processability of organic molecular crystals plays a pivotal role in shaping their utility in real‐world applications. From growth methodologies to fabrication techniques, the ability to precisely machine these crystals opens new avenues for engineering materials with enhanced functionality. These processing methods enhance the versatility of organic crystals, allowing their integration into various devices and technologies, and further expanding the potential applications. This review aims to provide a concise overview of the current landscape in the study of dynamic organic molecular crystals, with an emphasis on the interconnected themes of operability and processability.

Capturing the Interplay Between TADF and RTP Through Mechanically Flexible Polymorphic Optical Waveguides

AbstractPolymorphism plays a pivotal role in generating a range of crystalline materials with diverse photophysical and mechanical attributes, all originating from the same molecule. Here, we showcase two distinct polymorphs: green (GY) emissive and orange (OR) emissive crystals of 5′‐(4‐(diphenylamino)phenyl)‐[2,2′‐bithiophene]‐5‐carbaldehyde (TPA‐CHO). These polymorphs display differing optical characteristics, with GY exhibiting thermally activated delayed fluorescence (TADF) and OR showing room temperature phosphorescence (RTP). Additionally, both polymorphic crystals display mechanical flexibility and optical waveguiding capabilities. Leveraging the AFM‐tip‐based mechanophotonics technique, we position the GY optical waveguide at varying lengths perpendicular to the OR waveguide. This approach facilitates the exploration of the interplay between TADF and RTP phenomena by judiciously controlling the optical path length of crystal waveguides. Essentially, our approach provides a clear pathway for understanding and controlling the photophysical processes in organic molecular crystals, paving the way for advancements in polymorphic crystal‐based photonic circuit technologies.

Capturing the Interplay Between TADF and RTP Through Mechanically Flexible Polymorphic Optical Waveguides.

Polymorphism plays a pivotal role in generating a range of crystalline materials with diverse photophysical and mechanical attributes, all originating from the same molecule. Here, we showcase two distinct polymorphs: green (GY) emissive and orange (OR) emissive crystals of 5'-(4-(diphenylamino)phenyl)-[2,2'-bithiophene]-5-carbaldehyde (TPA-CHO). These polymorphs display differing optical characteristics, with GY exhibiting thermally activated delayed fluorescence (TADF) and OR showing room temperature phosphorescence (RTP). Additionally, both polymorphic crystals display mechanical flexibility and optical waveguiding capabilities. Leveraging the AFM-tip-based mechanophotonics technique, we position the GY optical waveguide at varying lengths perpendicular to the OR waveguide. This approach facilitates the exploration of the interplay between TADF and RTP phenomena by judiciously controlling the optical path length of crystal waveguides. Essentially, our approach provides a clear pathway for understanding and controlling the photophysical processes in organic molecular crystals, paving the way for advancements in polymorphic crystal-based photonic circuit technologies.

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.

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.

Social Self-Sorting of Quasi-Racemates: A Unique Approach for Dual-Pore Molecular Crystals.

Despite recent advances in porous organic molecular crystals, the engineering of dual-pore systems within the intermolecular voids remains a significant challenge. In this study, we have achieved the crystallization-induced social self-sorting of "quasi-racemic" dialdehydes into a macrocyclic imine. X-ray crystallographic analysis unambiguously characterizes the resulting structure as incorporating two quasi-racemate pairs with four diamine molecules. Notably, different alkyl substituents on the quasi-racemates afford two types of one-dimensional pores within the macrocyclic imine crystal. The different adsorption properties of these pores were substantiated through adsorption experiments. An intriguing helical arrangement of guest molecules was observed within one of the pores. This study provides pioneering evidence that the social self-sorting of quasi-racemates offers a new methodology for creating dual-functional supramolecular materials.

Solar overall water-splitting by a spin-hybrid all-organic semiconductor

Direct solar-to-hydrogen conversion from pure water using all-organic heterogeneous catalysts remains elusive. The challenges are twofold: (i) full-band low-frequent photons in the solar spectrum cannot be harnessed into a unified S1 excited state for water-splitting based on the common Kasha-allowed S0 → S1 excitation; (ii) the H+ → H2 evolution suffers the high overpotential on pristine organic surfaces. Here, we report an organic molecular crystal nanobelt through the self-assembly of spin-one open-shell perylene diimide diradical anions (:PDI2-) and their tautomeric spin-zero closed-shell quinoid isomers (PDI2-). The self-assembled :PDI2-/PDI2- crystal nanobelt alters the spin-dependent excitation evolution, leading to spin-allowed S0S1 → 1(TT) → T1 + T1 singlet fission under visible-light (420 nm~700 nm) and a spin-forbidden S0 → T1 transition under near-infrared (700 nm~1100 nm) within spin-hybrid chromophores. With a triplet-triplet annihilation upconversion, a newly formed S1 excited state on the diradical-quinoid hybrid induces the H+ reduction through a favorable hydrophilic diradical-mediated electron transfer, which enables simultaneous H2 and O2 production from pure water with an average apparent quantum yield over 1.5% under the visible to near-infrared solar spectrum.

Machine-Learned Potentials by Active Learning from Organic Crystal Structure Prediction Landscapes.

A primary challenge in organic molecular crystal structure prediction (CSP) is accurately ranking the energies of potential structures. While high-level solid-state density functional theory (DFT) methods allow for mostly reliable discrimination of the low-energy structures, their high computational cost is problematic because of the need to evaluate tens to hundreds of thousands of trial crystal structures to fully explore typical crystal energy landscapes. Consequently, lower-cost but less accurate empirical force fields are often used, sometimes as the first stage of a hierarchical scheme involving multiple stages of increasingly accurate energy calculations. Machine-learned interatomic potentials (MLIPs), trained to reproduce the results of ab initio methods with computational costs close to those of force fields, can improve the efficiency of the CSP by reducing or eliminating the need for costly DFT calculations. Here, we investigate active learning methods for training MLIPs with CSP datasets. The combination of active learning with the well-developed sampling methods from CSP yields potentials in a highly automated workflow that are relevant over a wide range of the crystal packing space. To demonstrate these potentials, we illustrate efficiently reranking large, diverse crystal structure landscapes to near-DFT accuracy from force field-based CSP, improving the reliability of the final energy ranking. Furthermore, we demonstrate how these potentials can be extended to more accurately model structures far from lattice energy minima through additional on-the-fly training within Monte Carlo simulations.

Harmonic and anharmonic studies on THz spectra of two vanillin polymorphs

Polymorphism commonly exists in organic molecular crystals. The fingerprint features in low-frequency vibrational range are important information reflecting different intermolecular interactions of polymorphs. Interpreting these features is very helpful to understand vibrational property of polymorphs and reveal the thermodynamic stability. In this work, the low-frequency vibrations of form I and II of vanillin are investigated using terahertz time-domain spectroscopy. Static DFT calculation and ab initio molecular dynamics (AIMD) are employed to interpret their low-frequency vibrations of both forms in harmonic and anharmonic ways, respectively. Their low-frequency vibration characteristics in harmonic calculations are discussed, and anharmonic mode couplings between OH bond stretch and the stretching and bending motion of hydrogen bonds are uncovered. Moreover, the thermodynamic energies including electronic potential energy and vibrational/kinetic energy arising from nuclear motions are calculated. The result reveals that the stability order of the two forms is mainly dependent on their electric potential energy difference.

Knowledge distillation of neural network potential for molecular crystals.

Organic molecular crystals exhibit various functions due to their diverse molecular structures and arrangements. Computational approaches are necessary to explore novel molecular crystals from the material space, but quantum chemical calculations are costly and time-consuming. Neural network potentials (NNPs), trained on vast amounts of data, have recently gained attention for their ability to perform energy calculations with accuracy comparable to quantum chemical methods at high speed. However, NNPs trained on datasets primarily consisting of inorganic crystals, such as the Materials Project, may introduce bias when applied to organic molecular crystals. This study investigates the strategies to improve the accuracy of a pre-trained NNP for organic molecular crystals by distilling knowledge from a teacher model. The most effective knowledge transfer was achieved when fine-tuning using only soft targets, i.e., the teacher model's inference values. As the ratio of hard target loss increased, the efficiency of knowledge transfer decreased, leading to overfitting. As a proof of concept, the NNP created through knowledge distillation was used to predict elastic properties, resulting in improved accuracy compared to the pre-trained model.

Multifunctional single-component organic molecular materials: ferroelectricity, negative thermal expansion, and polymorphism

The evolution of research on ferroelectricity and unusual thermal expansion properties in organic molecular crystals and their existence in polymorphic forms have been highlighted to pinpoint the importance of such materials in organic electronics.

Molecular stacking mode-directed mechanical compliance and room-temperature phosphorescence achieved by polymorphic 4-cyanobenzamide crystals

Two 4-cyanobenzamide polymorphs are identified by well-organization of hydrogen-bond interactions, exhibiting molecular stacking mode-dependent mechanical responses and RTP emissions.

Hybrid and composite materials of organic crystals.

Organic molecular crystals have historically been viewed as delicate and fragile materials. However, recent studies have revealed that many organic crystals, especially those with high aspect ratios, can display significant flexibility, elasticity, and shape adaptability. The discovery of mechanical compliance in organic crystals has recently enabled their integration with responsive polymers and other components to create novel hybrid and composite materials. These hybrids exhibit unique structure-property relationships and synergistic effects that not only combine, but occasionally also enhance the advantages of the constituent crystals and polymers. Such organic crystal composites rapidly emerge as a promising new class of materials for diverse applications in optics, electronics, sensing, soft robotics, and beyond. While specific, mostly practical challenges remain regarding scalability and manufacturability, being endowed with both structurally ordered and disordered components, the crystal-polymer composite materials set a hitherto unexplored yet very promising platform for the next-generation adaptive devices. This Perspective provides an in-depth analysis of the state-of-the-art in design strategies, dynamic properties and applications of hybrid and composite materials centered on organic crystals. It addresses the current challenges and provides a future outlook on this emerging class of multifunctional, stimuli-responsive, and mechanically robust class of materials.

Biomimetic synthesis of single-crystalline anhydrous xanthine nanoplates in an aqueous solution with high reflectivity.

Biogenic purine crystals can function in vision as light scatters, mirrors, and multilayer reflectors and produce structural colors or depolarization for camouflage. Xanthine crystals form irregular multifocal mirrors in the median ocellus of Archaeognatha. It is important to broaden the study of crystallization strategies to obtain organic crystals with purine rings in the laboratory. In this work, a facile one-step synthesis route to fabricate bio-inspired xanthine crystals is reported for the first time. The obtained rhomboidal xanthine nanoplates have similar morphology and size to biogenic xanthine crystals. Their length and thickness are about 2-4 μm and 50 nm, respectively. Lattice parameters, crystal structure, formation mechanism and optical properties of synthetic single-crystalline xanthine nanoplates were investigated in detail in this work. The obtained xanthine nanoplate crystals are proposed to be anhydrous xanthine with monoclinic symmetry, and the xanthine nanoplates mainly expose the (100) plane. It is proposed that the anhydrous xanthine nanoplates are formed via an amorphous xanthine intermediate precursor. The synthetic anhydrous xanthine nanoplates exhibit excellent optical properties, including high diffuse reflectivity, strong depolarization and pearlescent luster. This work provides a new design to synthesize bio-inspired organic molecular crystals with excellent optical properties.

Large polarons in two-dimensional fullerene networks: the crucial role of anisotropy in charge transport.

The recent synthesis of a two-dimensional quasi-hexagonal-phase monolayer network of C60 molecules, known as qHPC60, holds significant promise for future semiconductor applications. However, the mechanism behind charge transport in these networks remains unknown. In this study, we developed a Holstein-Peierls Hamiltonian model to investigate charge transport in qHPC60, incorporating both local and non-local electron-phonon couplings. Our computational approach involved identifying suitable semi-empirical parameters to realize the formation of stable polarons in this material. The results unveiled the formation of stable large polarons as the primary carriers in the charge transport throughout qHPC60. To explore polaron transport properties, we conducted dynamic simulations within the picosecond time scale while subjecting the system to an external electric field. Our analysis emphasized the substantial influence of anisotropy on shaping mobile polarons, with an anisotropy coefficient of at least 50%. The polarons exhibited velocities within the acoustic regime ranging from 0.5-1.5 nm ps-1. While these velocities are comparable to those observed in high-end organic molecular crystals, they are considerably lower than those in graphene and conducting polymers. With qHPC60 possessing a semiconducting band gap of approximately 1.6 eV, our findings shed light on its potential application in flat electronics, overcoming the null-gap predicament of graphene.

Influence of N-protonation on electronic properties of acridine derivatives by quantum crystallography.

Applications of 9-aminoacridine (9aa) and its derivatives span fields such as chemistry, biology, and medicine, including anticancer and antimicrobial activities. Protonation of such molecules can alter their bioavailability as weakly basic drugs like aminoacridines exhibit reduced solubility at high pH levels potentially limiting their effectiveness in patients with elevated gastric pH. In this study, we analyse the influence of protonation on the electronic characteristics of the molecular organic crystals of 9-aminoacridine. The application of quantum crystallography, including aspherical atom refinement, has enriched the depiction of electron density in the studied systems and non-covalent interactions, providing more details than previous studies. Our experimental results, combined with a topological analysis of the electron density and its Laplacian, provided detailed descriptions of how protonation changes the electron density distribution around the amine group and water molecule, concurrently decreasing the electron density at bond critical points of N/O-H bonds. Protonation also alters the molecular architecture of the systems under investigation. This is reflected in different proportions of the N⋯H and O⋯H intermolecular contacts for the neutral and protonated forms. Periodic DFT calculations of the cohesive energies of the crystal lattice, as well as computed interaction energies between molecules in the crystal, confirm that protonation stabilises the crystal structure due to a positive synergy between strong halogen and hydrogen bonds. Our findings highlight the potential of quantum crystallography in predicting crystal structure properties and point to its possible applications in developing new formulations for poorly soluble drugs.