RESUMEN

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.

RESUMEN

The development of smart, stimuli-responsive materials has received increased attention in the past decade for their applications as sensing technologies. This commentary discusses a timely topical review by Kato [(2024). IUCrJ, 11, 442-452] on the fabrication of multi-stimuli responsive crystals comprised of luminescent platinum(II) complexes, which exhibit intriguing chromic phenomena in response to stimuli.

RESUMEN

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.

RESUMEN

One of the typical haptic elements are natural hairy structures that animals and plants rely on for feedback. Although these hair sensors are an admirable inspiration, the development of active flow sensing components having low elastic moduli and high aspect ratios remains a challenge. Here, we report a new sensing approach based on a flexible, thin and optically transmissive organic crystal of high aspect ratio, which is stamped with fluorescent dye for tracking. When subjected to gas flow and exposed to laser, the crystal bends due to exerted pressure and acts as an optical flow (hair) sensor with low detection limit (≈1.578 m s-1 ) and fast response time (≈2.70 s). The air-flow-induced crystal deformation and flow dynamics response are modelled by finite element analysis. Due to having a simple design and being lightweight and mechanically robust this prototypical crystal hair-like sensor opens prospects for a new class of sensing devices ranging from wearable electronics to aeronautics.

RESUMEN

Organic crystals that respond to external stimuli are interesting for the design of smart materials. Here, we show that molecular engineering can transform simple naphthalidenimine-boron complexes─known for their exciting photophysical properties─into functional materials that exhibit thermosalience and thermal-luminescence switching. Detailed crystallographic and spectroscopic investigations revealed the role of subtle molecular parameters in deciphering charge-transfer interactions, which in turn imparted dynamic properties to the crystals. The simultaneous observation of thermally induced jumping and luminescence switching makes these crystals ideal for optoelectronic applications.

RESUMEN

A new 1D-coordination polymer [Co(Piv)2(NH2(CH2)6NH2)]n (1, Piv is Me3CCO2- anion) was obtained, the mononuclear fragments {Co(O2CR)2} within which are linked by µ-bridged molecules of hexamethylenediamine (NH2(CH2)6NH2). For this compound, two different monoclinic C2/c (α-1) and P2/n (ß-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and ß-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom ("octahedral CoN2O4 around the metal center at room temperature" → "pseudo-tetrahedral CoN2O2 at 150 K"). The SPT was confirmed by DSC in the temperature range 210-150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,ß,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χMT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χMT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χMT(T) curve for 1 was simulated in the temperature range of 2-150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe.

Asunto(s)

Cobalto , Frío , Cobalto/química , Cristalografía por Rayos X , Transición de Fase

RESUMEN

Thus far, reports about the transformations for dynamic crystals of supramolecular coordination systems mainly include single-crystal-to-single-crystal reactions, and solvent-mediated processes. This Concept focuses on the mechanisms for solvent-mediated structural transformations of dynamic crystals, which can be classified into two categories, that is, core-on-shell and core-to-core. The core-on-shell mechanism means that the core of the new crystal is generated from the shell of original crystal, being concomitant with the dissolution of the mother crystal. In contrast, for the core-to-core case, the growth of new crystal core and the dissolution of original crystal core will proceed simultaneously, but they are physically separated. Herein, the two mechanisms are elucidated in detail, with some typical examples from recent advances.

RESUMEN

Currently, no unequivocal evidence is given for elucidation of "black box" during the structural transformations of dynamic crystalline materials. Here, three types of mechanisms are revealed for such transformations through X-ray diffraction and optical microscopy; namely, single-crystal to single-crystal (SC-SC), as well as "core-to-core" and "core-on-shell" processes. As confirmed by time-lapse optical microscopy, the latter two cases can be properly ascribed as partial recrystallization processes, while the former one is a continuous process with two different crystal lattices simultaneously maintained in one single crystal. Interestingly, these three distinct pathways can be exquisitely realized by changing only the halogen substituent (from -F, -Cl, to -Br) of the organic ligands in the coordination supramolecular systems.

RESUMEN

Three polymorphs of a di-chloro-N-salicylideneaniline derivative show visually impressive jumping and sudden blasting behaviours on heating due to phase transitions.