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Despite having superior transport properties, lack of mechanical flexibility is a major drawback of crystalline molecular semiconductors as compared to their polymer analogues. Here single crystals of an organic semiconductor are reported that are not only flexible but exhibit systematic tuning of bandgaps, fluorescence lifetime, and emission wavelengths upon elastically bending. Spatially resolved fluorescence lifetime imaging and confocal fluorescence microscopy reveals systematic trends in the lifetime decay across the bent crystal region along with shifts in the emission wavelength. From the outer arc to the inner arc of the bent crystal, a significant decrease in the lifetime of ≈1.9 ns is observed, with a gradual bathochromic shift of ≈10 nm in the emission wavelength. For the crystal having a bandgap of 2.73 eV, the directional stress arising from bending leads to molecular reorientation effects and variations in the extent of intermolecular interactions- which are correlated to the lowering of bandgap and the evolution of the projected density of states. The systematic changes in the interactions quantified using electron density topological analysis in the compressed inner arc and elongated outer arc region are correlated to the non-radiative decay processes, thus rationalizing the tuning of fluorescence lifetime.
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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.
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The structural dynamics involved in the mechanical flexibility of molecular crystals and the internal stress in such flexible materials remain obscure. Here, the study reports an elastically bending lipidated molecular crystal that shows systematic shifts in characteristic vibrational frequencies across the bent crystal region - revealing the nature of structural changes during bending and the local internal stress distribution. The blueshifts in the bond stretching modes (such as CâO and C-H modes) in the inner arc region and redshifts in the outer arc region of the bent crystals observed via micro-Raman mapping are counterintuitive to the bending models based on intermolecular hydrogen bonds. Correlating these shifts with the trends observed from high-pressure Raman studies on the crystal reveals the local stress difference between the inner arc and outer arc regions of the bent crystal to be ≈2 GPa, more than an order of magnitude higher than the previously proposed value in elastically bending crystals. High local internal stress can have direct ramifications on the properties of molecular piezoelectric energy harvesters, actuators, semiconductors, and flexible optoelectronic materials.
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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.
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The dense and ordered molecular arrangements endow dynamic molecular crystals with fast response, rapid energy conversion, low energy dissipation, and strong coupling between heat/light and mechanical energy. Most of the known dynamic crystals can only respond to a single stimulus, and materials that can respond to multiple stimuli are rare. Here, we report an organic crystalline material that can be bent plastically and is also thermosalient, as its crystals can move when they undergo a reversible phase transition. The crystals transmit light regardless of their shape or crystalline phase. The combination of light transduction and reversible thermomechanical deformation provides an opportunity to switch the waveguiding capability of the material in a narrow temperature range, which holds a tremendous potential for applications in heat-averse electronic components, such as central processing units. Unlike existing electronics, the material we report here is completely organic and therefore much lighter, potentially reducing the overall weight of electronic circuits.
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The program FlÉX (flexural É for xtals) has been developed for a quick, easy and accurate evaluation of the maximum deformation reached in flexible crystals from a simple optical microscope picture. The program takes advantage of computer vision libraries to find the contours of a bent crystal and fit these to semicircles. It can then calculate the theoretical maximum deformation along its long axis using equations from the Euler-Bernoulli beam theory.
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Organic single crystals quickly emerge as dense yet light and nearly defect-free media for emissive elements. Integration of functionalities and control over the emissive properties is currently being explored for a wide range of these materials to benchmark their performance against organic emissive materials diluted in powders or films. Here, we report mechanically flexible emissive chiral organic crystals capable of an unprecedented combination of fast, reversible, and low-fatigue responses. UV-excited single crystals of both enantiomers of the material, 4-chloro-2-(((1-phenylidene)imino)methyl)phenol, exhibit a drastic yet reversible change in the emission color from green to orange-yellow within a second and can be cycled at least 2000â times. The photoresponse was found to depend strongly on the excitation intensity and temperature. Combining chirality, mechanical compliance, rapid emission switching, multiple responses, and writability by UV light, this material provides a unique and versatile platform for developing organic crystal-based materials for on-demand signal transfer, information storage, and cryptography.
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Aiming to solve the trade-off of "room-temperature phosphorescence (RTP)-flexibility" in principle, organic RTP crystals with elastic/plastic deformation are realized. These properties are mainly due to the divisional aggregation structures of aromatics and alkoxy chains, and can be modulated by the controllable molecular configurations. The longest RTP lifetime of 972.3 ms is achieved as the highest record for organic flexible crystals. Plastic crystals with persistent RTP are realized, which can be applied into biomedical optical technologies by afterglow delivery. Moreover, the relationship among elastic/plastic deformation, RTP property, and aggregated structures is established. The elastic/plastic deformation is mainly determined by the difference of interaction energies from the aromatics and the alkoxy chains. For the BP-OR series with twisted configurations, the alkoxy chain with the middle length is favorable for the RTP property, while the strength of the π-π coupling is the cruical factor to the RTP property of the Xan-OR series with planar skeletons. A new way to promote the development of flexible RTP crystals, by modulation of aggregated structures as well as rational distribution of intermolecular interactions, is explored.
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We report the construction of an organic crystal multiplexer using three chemically and optically different acicular, flexible organic crystals for a broadband, visible light signal transportation. The mechanical integration of a highly flexible crystal waveguide of (Z)-2-(3,5-bis(trifluoromethyl)phenyl)-3-(7-methoxybenzo[c][1,2,5]thiadiazol-4-yl)acrylonitrile (BTD2CF3 ) displaying bright yellow (λ1 ) fluorescence with blue-emitting (λ2 ) BPP and cyan emitting (λ3 ) DBA crystals using AFM-tip provides a composite organic crystal multiplexer. The constructed hybrid single crystal multiplexer effectively transduces three optical signals (λ1 +λ2 +λ3 ) covering the 420-750â nm region as a composite output signal. The presented proof-of-principle experiment demonstrates the real potential of organic flexible crystal waveguides for visible light communication technologies.
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Flexible organic crystals with unique mechanical properties and excellent optical properties are of paramount significance for their wide applications in various research fields such as adaptive optics and soft robotics. However, low-temperature-resistant flexible organic crystal with circularly polarized luminescence (CPL) has never been reported. Herein, chiral organic crystals with CPL activity and low-temperature flexibility (77â K) are fabricated by the solvent diffusion method from chiral Schiff base, S(R)-4-bromo-2-(((1-phenylethyl)imino)methyl)phenol (S(R)-BPEMP). The corresponding chirooptical properties for the two enantiomeric crystals were thoroughly investigated, including the measurements of circular dichroism (CD) and CPL. To the best of our knowledge, this is the first report on low-molecular-weight flexible organic crystals with CPL activity, and we believe that the results will give a new impetus to the research of organic crystals.
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Zeolitic imidazolate frameworks (ZIFs) have long been recognized as a prominent subset of the metal-organic framework (MOF) family, in part because of their ease of synthesis and good thermal and chemical stability, alongside attractive properties for diverse potential applications. Prototypical ZIFs like ZIF-8 have become embodiments of the significant promise held by porous coordination polymers as next-generation designer materials. At the same time, their intriguing property of experiencing significant structural changes upon the application of external stimuli such as temperature, mechanical pressure, guest adsorption, or electromagnetic fields, among others, has placed this family of MOFs squarely under the umbrella of stimuli-responsive materials. In this review, we provide an overview of the current understanding of the triggered structural and electronic responses observed in ZIFs (linker and bond dynamics, crystalline and amorphous phase changes, luminescence, etc.). We then describe the state-of-the-art experimental and computational methodology capable of shedding light on these complex phenomena, followed by a comprehensive summary of the stimuli-responsive nature of four prototypical ZIFs: ZIF-8, ZIF-7, ZIF-4, and ZIF-zni. We further expose the relevant challenges for the characterization and fundamental understanding of responsive ZIFs, including how to take advantage of their flexible properties for new application avenues.
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We report the first organic semiconductor crystal with a unique combination of properties that can be used as a multifunctional optoelectronic device. Mechanically flexible single crystals of 9,10-bis(phenylethynyl)anthracene (BPEA) can function as a phototransistor, photoswitch, and an optical waveguide. The material can exist as two structurally different solid phases, with single crystals of one of the phases being elastic at room temperature while those of the other are brittle and become plastic at higher temperature. The output and transfer characteristics of the devices were characterized by measuring the generation and temporal response of the switching of the photogenerated current. The current-voltage characteristics of both phases exhibit linearity and symmetry about the positive and negative voltages. The crystals transmit light in the telecommunications range with significantly low optical loss for an organic crystalline material.
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The advent of molecular crystals as "smart" nanophotonic components namely, organic waveguides, resonators, lasers, and modulators are drawing wider attention of solid-state materials scientists and microspectroscopists. Crystals are usually rigid, and undeniably developing next-level crystalline organic photonic circuits of complex geometries demands using mechanically flexible crystals. The mechanical shaping of flexible crystals necessitates applying challenging micromanipulation methods. The rise of atomic force microscopy as a mechanical micromanipulation tool has increased the scope of mechanophotonics and subsequently, crystal-based microscale organic photonic integrated circuits (OPICs). The unusual higher adhesive energy of the flexible crystals to the surface than that of crystal shape regaining energy enables carving intricate crystal geometries using micromanipulation. This perspective reviews the progress made in a key research area developed by my research group, namely mechanophotonics-a discipline that uses mechanical micromanipulation of single-crystal optical components, to advance nanophotonics. The precise fabrication of photonic components and OPICs from both rigid and flexible microcrystal via AFM mechanical operations namely, moving, lifting, cutting, slicing, bending, and transferring of crystals are presented. The ability of OPICs to guide, split, couple, and modulate visible electromagnetic radiation using passive, active, and energy transfer mechanism are discussed as well with recent literature examples.
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Precise mechanical processing of optical microcrystals involves complex microscale operations viz. moving, bending, lifting, and cutting of crystals. Some of these mechanical operations can be implemented by applying mechanical force at specific points of the crystal to fabricate advanced crystalline optical junctions. Mechanically compliant flexible optical crystals are ideal candidates for the designing of such microoptical junctions. A vapor-phase growth of naturally bent optical waveguiding crystals of 1,4-bis(2-cyanophenylethynyl)benzene (1) on a surface forming different optical junctions is presented. In the solid-state, molecule 1 interacts with its neighbors via CHâ â â N hydrogen bonding and π-π stacking. The microcrystals deposited at a glass surface exhibit moderate flexibility due to substantial surface adherence energy. The obtained network crystals also display mechanical compliance when cut precisely with sharp atomic force microscope cantilever tip, making them ideal candidates for building innovative T- and Δ-shaped optical junctions with multiple outputs. The presented micromechanical processing technique can also be effectively used as a tool to fabricate single-crystal integrated photonic devices and circuits on suitable substrates.
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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.
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Single crystals of optoelectronic materials that respond to external stimuli, such as mechanical, light, or heat, are immensely attractive for next generation smart materials. Here we report single crystals of a green fluorescent protein (GFP) chromophore analogue with irreversible mechanical bending and associated unusual enhancement of the fluorescence, which is attributed to the strained molecular packing in the perturbed region. Soft crystalline materials with such fluorescence intensity modulations occurring in response to mechanical stimuli under ambient pressure conditions will have potential implications for the design of technologically relevant tunable fluorescent materials.
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The design of molecular compounds that exhibit flexibility is an emerging area of research. Although a fair amount of success has been achieved in the design of plastic or elastic crystals, realizing multidimensional plastic and elastic bending remains challenging. We report herein a naphthalidenimine-boron complex that showed size-dependent dual mechanical bending behavior whereas its parent Schiff base was brittle. Detailed crystallographic and spectroscopic analysis revealed the importance of boron in imparting the interesting mechanical properties. Furthermore, the luminescence of the molecule was turned-on subsequent to boron complexation, thereby allowing it to be explored for multimode optical waveguide applications. Our in-depth study of the size-dependent plastic and elastic bending of the crystals thus provides important insights in molecular engineering and could act as a platform for the development of future smart flexible materials for optoelectronic applications.
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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.
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Mechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one-dimensional (1D) coordination polymer. The compound [Zn(µ-Cl)2 (3,5-dichloropyridine)2 ]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 180°. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material.
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Crystalline coordination polymers tend to be brittle and inelastic, however, we now describe a family of such compounds that are capable of displaying mechanical elasticity in response to external pressure. The design approach successfully targets structural features that are critical for producing the desired mechanical output. The elastic crystals all comprise 1D cadmium(II) halide polymeric chains with adjacent metal centres bridged by two halide ions resulting in the required stacking interactions and short "4â Å" crystallographic axes. These polymeric chains (structural "spines") are further organized via hydrogen bonds and halogen bonds perpendicular to the direction of the chains. By carefully altering the strength and the geometry of these non-covalent interactions, we have demonstrated that it is possible to control the extent of elastic bending in crystalline coordination compounds.