Negative Linear Compressibility Research Articles

Anisotropic materials with abnormal Poisson's ratios and acoustic velocities.

Isotropic materials are required to adhere to various mechanical principles due to their limited thermal stability. For instance, it is essential for Poisson's ratio to be within the range of -1 to 0.5, and the longitudinal wave velocity must exceed the transverse wave velocity. Nevertheless, perfect crystals, as anisotropic materials, have the ability to defy conventional rules. Through the integration of high-throughput processes and first-principles calculations, a comprehensive exploration of known materials was conducted, resulting in the establishment of a database featuring an extreme anisotropic mechanism. This included the identification of abnormal Poisson's ratios (with the directional Poisson's ratio ranging from -3.00 to 3.67), the discovery of extreme negative linear compressibility, the determination of the upper and lower limits of the sound velocity, and other associated properties. Several materials with abnormal Poisson's ratios (<-1 or >0.5) were listed, and their peculiar mechanical behavior, wherein the volume decreased counterintuitively with uniaxial tension, was discussed. Finally, this study focused on the velocities of longitudinal and transverse waves, with specific emphasis on materials exhibiting transverse wave velocities that exceeded the longitudinal wave velocities.

Negative Linear Compressibility and Interlayer Gap Closure in Layered Rare-Earth Hydroxyhalide (YCl(OH)2) under High Pressure.

Layered materials have attracted extensive attention due to their exceptional physical and chemical properties. Understanding the structural evolution of such materials under high pressure is crucial for the development of new functional materials. In this study, the structure evolution of the synthesized layered rare-earth hydroxyhalide YCl(OH)2 under high pressures up to approximately 9.4 GPa was explored by using a diamond anvil cell combined with synchrotron single-crystal X-ray diffraction. Simultaneously, high-pressure Raman spectroscopy experiment was conducted to 10.3 GPa. Our findings indicate that YCl(OH)2 maintains its symmetry within the experimental pressure range. The pressure-volume data of YCl(OH)2 were fitted to the third-order Birch-Murnaghan equation of state (EoS) to derive its EoS parameters including zero-pressure unit-cell volume (VT0), isothermal bulk modulus (KT0), and its pressure derivative (K'T0): VT0 = 142.47 (1) Å3, KT0 = 38.2 (18) GPa, and K'T0 = 9.8 (1). However, the unit-cell parameters a, b, and c exhibit a distinct compressional behavior, with the a-axis being the most compressible and the b-axis being the least. Particularly noteworthy is the observation that YCl(OH)2 displays a negative linear compressibility along the b-axis within the pressure range of 0.4-5.3 GPa. Further detailed structure refinement and Raman spectroscopy analyses indicate that the anomalous behavior of the b-axis could be attributed to the formation of the O-H···O hydrogen bonding chains along the b direction. Moreover, the coordination number of Y3+ increased from 8 to 9 as the pressure reached 5.3 GPa due to the reduction of the interlayer spacing upon compression, ultimately leading to the closure of the interlayer gap.

Hydrogen-bond-modulated negative linear compressibility in a V-shaped molecular crystal.

A material with the "hidden" negative linear compressibility (NLC) will expand along a specific crystal direction upon uniformly compression to a critical pressure; such materials are thought to be promising candidates for non-linear actuators, switches and sensors. Herein, we use density functional theory (DFT) calculations to uncover the hidden NLC in a V-shaped molecular crystal, bis(5-amino-1,2,4-triazol-3-yl)methane (BATZM). The calculations indicate that the crystal is normally compressed over the pressure range of 0-3 GPa while it expands along the b-axis when the external hydrostatic pressure exceeds 3 GPa. The compressive behavior of the BATZM crystal is modulated by inter-molecular hydrogen bonds, which act as highly compressible springs at low pressures but robust struts at high pressures. Hence, the crystal prefers to compress the hydrogen bonds coupled with PLC at first and flatten the molecules, coupled with later NLC to resist the increasing external pressure. The compressive behavior of BATZM provides a strategy to design more hidden NLC materials via the rational use of the hydrogen bonds.

Negative linear compressibility exhibited by the hybrid perovskite [(NH2)3C]Er(HCO2)2(C2O4).

Extended framework materials with specific topologies can exhibit unusual mechanical behaviour, such as expanding in one direction under hydrostatic (uniform) pressure, known as negative linear compressibility (NLC). Here, two hybrid perovskite frameworks with winerack structures, a known NLC topology, are investigated under pressure. [C(NH2)3]Er(HCO2)2(C2O4) exhibits NLC from ambient pressure to 2.63(10) GPa and is the first reported NLC hybrid perovskite from ambient pressure. However, isostructural [(CH3)2NH2]Er(HCO2)2(C2O4) instead compresses relatively moderately along all axes before it undergoes a phase transition above 0.37(10) GPa. The differences in the mechanical properties can be interpreted from differences in host-guest interactions within these frameworks, primarily their hydrogen bond networks.

Metal-free negative linear compressibility (NLC) material - the cocrystal of 1,2-bis(4-pyridyl)ethane and fumaric acid.

Materials that show significant negative linear compressibility (NLC) reported so far suffer from a number of shortcomings that affect their applicability. The cocrystal of 1,2-bis(4-pyridyl)ethane and fumaric acid, which exhibits exceptional NLC behaviour, overcomes these problems and sets the foundation for the development of environmentally friendly metal-free NLC materials.

Negative linear compressibility and strong enhancement of emission in Eu[Ag(CN)2]3·3H2O under pressure.

The framework material Eu[Ag(CN)2]3·3H2O exhibits a negative linear compressibility (NLC) of -4.2(1) TPa-1 over the largest pressure range yet observed (0-8.2 GPa). High-pressure single-crystal X-ray diffraction data show that the rapid contraction of the Kagome silver layers under compression causes the wine-rack lattice to expand along the c-axis. The hydrogen bonds between the water molecules and the main frameworks constrain the structural deformation under pressure and eventually a weak NLC effect generated. Furthermore, we found that the pressure-induced emission intensity increases almost 800-fold at 4.0 GPa, followed by a gradual decrease and disappearance at 8.1 GPa. Under compression, high pressure significantly tunes the triplet level positions near the Eu3+ ions, and horizontal displacement between a quenching excited state and the excited levels of Eu3+ facilitates the energy transfer process to the 5D0 excited state and limits the nonradiative corssover at elevated pressures, thus increasing the emission intensity. In addition, we observe a gradual band gap reduction with increasing pressure, and the sample could not be returned to the initial state after the pressure was completely released. By controlling the structural flexibility, we observe a coupled NLC and pressure-induced strong enhancement of the emission properties of Eu[Ag(CN)2]3·3H2O, which provides a new route for the design of new optical devices with intriguing luminescence properties under extreme environments.

Crystalline porous organic salts.

Crystalline porous organic salts (CPOSs), formed by the self-assembly of organic acids and organic bases through ionic bonding, possess definite structures and permanent porosity and have rapidly emerged as an important class of porous organic materials in recent years. By rationally designing and controlling tectons, acidity/basicity (pKa), and topology, stable CPOSs with permanent porosity can be efficiently constructed. The characteristics of ionic bonds, charge-separated highly polar nano-confined channels, and permanent porosity endow CPOSs with unique physicochemical properties, offering extensive research opportunities for exploring their functionalities and application scenarios. In this review, we systematically summarize the latest progress in CPOS research, describe the synthetic strategies for synthesizing CPOSs, delineate their structural characteristics, and highlight the differences between CPOSs and hydrogen-bonded organic frameworks (HOFs). Furthermore, we provide an overview of the potential applications of CPOSs in areas such as negative linear compression (NLC), proton conduction, rapid transport of CO2, selective and rapid transport of K+ ions, atmospheric water harvesting (AWH), gas sorption, molecular rotors, fluorescence modulation, room-temperature phosphorescence (RTP) and catalysis. Finally, the challenges and future perspectives of CPOSs are presented.

Prediction of ternary alkaline-earth metal Sn(II) and Pb(II) chlorides with potential applications as p-type transparent conductors.

Non-metallic Sn(II) and Pb(II) compounds, particularly those with p-type properties, are essential functional materials due to their notable electronic arrangement and chemical characteristics. The presence of additional Sn(II) and Pb(II) chlorides is suggested by the existence of known Sn(II) and Pb(II) compounds. By utilizing first-principles calculations and swarm intelligence structure search techniques, we have predicted the existence of up to seven new ternary alkaline-earth metal chlorides: ABCl4 (where A = Sr and B = Sn or Pb) and AB2Cl6 (where A = Mg, Ca, or Ba and B = Sn, or A = Ca or Sr and B = Pb). These seven chlorides are in the divalent state. The interaction between Sn-5s (or Pb-6s) and Cl-3p in these compounds creates an anti-bonding effect in the upper valence bands, which enhances defect tolerance and promotes high p-type conductivity. These stable chlorides exhibit notable electronic properties, including wide band gaps ranging from 3.91 to 4.94 eV, broad hole effective masses ranging from 0.93 to 5.62 m0, and high valence band alignments ranging from 6.83 to 8.38 eV under vacuum. In particular, Ca/BaSn2Cl6 and CaPb2Cl6 have the potential to be used as p-type transparent conductors due to their favorable properties, including a lower hole effective mass (0.93 m0 for CaPb2Cl6) and higher ionization potentials (6.83/7.05 eV for Ba/CaSn2Cl6). Furthermore, the predicted CaPb2Cl6 crystal exhibits attenuated negative linear compressibility and negative zero-linear-compressibility along the c-axis in different pressure ranges due to its wine-rack structure. This report highlights potential applications for alkaline-earth metal Sn(II) and Pb(II) chlorides, including their use as transparent conductors, particularly p-type conductors.

Giant Negative Linear Compressibility, Isosymmetric Phase Transition, and Breathing Effect in a 3D Covalent Organic Framework

Giant Negative Linear Compressibility, Isosymmetric Phase Transition, and Breathing Effect in a 3D Covalent Organic Framework

Helical model of compression and thermal expansion

A negative linear temperature expansion and a negative linear compressibility were observed for imidazolium benzoate salt. Its strongly anisotropic strain induced by the temperature and pressure changes has been explained by the mechanism of H-bonded helices deformed in the structure. X-ray diffraction and vibrational spectroscopy were used to analyze interactions in the crystal. The Quantum Theory of Atoms in Molecules (QTAiM) approach was applied to analyze the hydrogen bonds and other interactions. In the salt under study, the interactions within the helix are substantially higher in energy than between helices. With decreasing temperature and increasing pressure, the value of the helix pitch increases while the value of the semi-major axis decreases, which results in the negative linear expansion and negative linear compression, respectively.

Flexible and gradually bonded metal organic framework coatings for atomic oxygen protection of polyimide films

Rapid development of coatings with atomic oxygen (AO) resistance, which benefit long-duration exploration mission in low earth orbit (LEO), poses a challenging requirement on flexible coatings with excellent bonding property. Metal organic framework (MOF) has abundant sites and organic–inorganic hybrid chemical composition, which displays potential in increasing AO resistance, flexibility and bonding property simultaneously. Here, we combined surface modification and spin-coating to prepare MIL-53(Al) (a kind of materials of Lavashir skeleton) coated polyimide (PI) thin film exhibiting excellent flexibility, bonding property and AO resistance, which had no cracks after bending 1000 times, had no peeling off and had only 12% erosion yield compared with pristine PI, verified by the bend test, cross-cut tape test and AO exposure experiment respectively. Also, the mechanism of homogeneous film formation was explained, in which MIL-53(Al) seed layer provided binding force between coating and substrate, and the microstructural transformation caused by breathing effect and negative linear compressibility (NLC) prevented the occurrence of coating cracking. This work extends the application range of MIL-53(Al), optimizes the application of MOFs film formation, and offers a new idea to protect the spacecrafts in LEO.

Negative linear compressibility in Se under pressure

Negative linear compressibility in Se under pressure

Negative linear compressibility and tuneable phase transition sequence in selenium and selected high-entropy oxides under high-pressure conditions via compressional rate control

Negative linear compressibility and tuneable phase transition sequence in selenium and selected high-entropy oxides under high-pressure conditions <i>via</i> compressional rate control

Negative Linear Compressibility of Formate Crystals from the Viewpoint of Quantum Electronic Pressure

In order to understand the phenomenon of negative linear compressibility (NLC) in organic crystals, it is necessary to investigate not only the structural features but also the electronic changes taking place under external hydrostatic pressure. It is also necessary to clarify which electronic properties allow the quantification and comparison of the compressibility of crystals. In our study, the crystal structures of sodium and cadmium formates under hydrostatic compression were modeled, as well as the α and β-phases of calcium formate. The changes in cell parameters and spatial dependences of the linear compressibility were analyzed, and the ranges of external pressure, which must be applied for NLC onset, were predicted for the sodium and α-calcium formates. Although the behavior of chemical bonds is not predicted by the sign or absolute value of the quantum electronic pressure, its relative change under external pressure clearly distinguishes the soft and rigid regions in a crystal. The relationship between the NLC values and the changes in quantum electronic pressure in the cavities of formate crystals was established.

Unveiling the multifaceted properties of a 3d covalent-organic framework: Pressure-induced phase transition, negative linear compressibility and auxeticity

High-pressure behavior and mechanical properties of a three-dimensional covalent-organic framework (NPN-1) were investigated by using different types of first principles molecular simulations. An irreversible pressure-induced first-order isosymmetric phase transition was predicted at 0.14 GPa. The subunit of NPN-1 retains its rigidity under pressure thanks to the strong covalent bonds. However, compression leads to significant tilting of the nitrophenyl groups. The mechanical properties of frameworks are highly anisotropic. Remarkably, both phases exhibit not only negative linear compressibility along the c-axis but also negative Poisson's ratio in certain directions. Detailed structural analysis revealed that the origin of the phase transition and anomalous mechanical properties of both phases are the wine-rack motif and strut-hinge mechanism. To the best of our knowledge, this study is the first report of such behavior in COFs, opening up new avenues for the exploration of COFs as materials for many promising applications.

A novel design of mechanical metamaterial incorporating multiple negative indexes

Mechanical metamaterials that combine multiple negative properties are rare, but have great appeal for applications in multipurpose devices. Herein, a novel metamaterial incorporating negative Poisson’s ratio, negative compressibility, and negative thermal expansion or swelling was proposed. The unit cell was designed by simulating the bond structure of lead monoxide crystals using elastic beams. Analytical models for the mechanical responses of the unit cell were established, and expressions for Young’s modulus, thermal expansion, Poisson’s ratio, and compressibility were derived and confirmed by numerical simulations. The results showed that the metamaterial not only displayed a negative Poisson’s ratio but also had negative linear and area compressibilities as well as negative linear, area, and volume thermal expansions if the geometric parameters were properly adjusted. Furthermore, metamaterials with negative linearity and area swelling were obtained experimentally by replacing the thermal expansion of the material with the water absorption expansion of a hydrogel. Such metamaterials with multiple negative indexes are expected to contribute to the feasibility of advanced multifunctional devices with mechanical, pressure, temperature, and moisture sensitivities.

Extreme flexibility and unusual piezomechanical properties of zinc-alkyl-based metal-organic frameworks: A first principles study

The behavior of three Zn-alkyl-based MOFs, ZnGA (Zn-Glutarate), ZnAA (Zn-Adipate), and ZAG-4 (Zinc Alky Gate), under hydrostatic compression has been investigated using first-principles DFT simulation, which has proven its reliability in previous studies. Due to the lack of the high pressure experimental data for ZnGA and ZnAA, the reliability of the simulation parameters was tested by taking ZAG-4, whose structural flexibility has been previously reported experimentally and computationally, as a benchmark. All three structures were found to exhibit elastic deformation under pressure up to 15 GPa, due to the flexibility of the alkyl chains that allow the structures to move without disrupting the metal-ligand coordination. Interestingly, the structures exhibit different mechanical properties, with ZAG-4 showing negative linear compressibility (NLC), ZnGA showing positive linear compressibility (PLC), and ZnAA showing zero linear compressibility (ZLC). The NLC in ZAG-4 is attributed to the proton transfer between phosphonate oxygen and water in the structure as previously reported, while the ZLC in ZnAA is due to a dumbbell-like structural motif formed by substructures displaying both NLC and PLC.

Chirality-Dependent Structural Transformation in Chiral 2D Perovskites under High Pressure.

Chiral perovskites have attracted considerable attention owing to their potential applications in spintronic- and polarization-based optoelectronic devices. However, the structural chirality/asymmetry transfer mechanism between chiral organic ammoniums and achiral inorganic frameworks is still equivocal, especially under extreme conditions, as the systematic structural differences between chiral and achiral perovskites have been rarely explored. Herein, we successfully synthesized a pair of new enantiomeric chiral perovskite (S/R-3PYEA)PbI4 (3PYEA2+ = C5NH5C2H4NH32+) and an achiral perovskite (rac-3PYEA)PbI4. Hydrostatic pressure was used, for the first time, to systematically investigate the differences in the structural evolution and optical behavior between (S/R-3PYEA)PbI4 and (rac-3PYEA)PbI4. At approximately 7.0 GPa, (S/R-3PYEA)PbI4 exhibits a chirality-dependent structural transformation with a bandgap "red jump" and dramatic piezochromism from translucent red to opaque black. Upon further compression, a previously unreported chirality-induced negative linear compressibility (NLC) is achieved in (S/R-3PYEA)PbI4. High-pressure structural characterizations and first-principles calculations demonstrate that pressure-driven homodirectional tilting of homochiral ammonium cations strengthens the interactions between S/R-3PYEA2+ and Pb-I frameworks, inducing the formation of new asymmetric hydrogen bonds N-H···I-Pb in (S/R-3PYEA)PbI4. The enhanced asymmetric H-bonding interactions further break the symmetry of (S/R-3PYEA)PbI4 and trigger a greater degree of in-plane and out-of-plane distortion of [PbI6]4- octahedra, which are responsible for chirality-dependent structural phase transition and NLC, respectively. Nevertheless, the balanced H-bonds incurred by equal proportions of S-3PYEA2+ and R-3PYEA2+ counteract the tilting force, leading to the absence of chirality-dependent structural transition, spectral "red jump", and NLC in (rac-3PYEA)PbI4.

Spacer-Dependent and Pressure-Tuned Structures and Optoelectronic Properties of 2D Hybrid Halide Perovskites.

Compared with their 3D counterparts, 2D hybrid organic-inorganic halide perovskites (HOIPs) exhibit enhanced chemical stabilities and superior optoelectronic properties, which can be further tuned by the application of external pressure. Here, we report the first high-pressure study on CMA2PbI4 (CMA = cylcohexanemethylammonium), a 2D HOIP with a soft organic spacer cation containing a flexible cyclohexyl ring, using UV-visible absorption, photoluminescence (PL) and vibrational spectroscopy, and synchrotron X-ray microdiffraction, all aided with density functional theory (DFT) calculations. Substantial anisotropic compression behavior is observed, as characterized by unprecedented negative linear compressibility along the b axis. Moreover, the pressure dependence of optoelectronic properties is found to be in strong contrast with those of 2D HOIPs with rigid spacer cations. DFT calculations help to understand the compression mechanisms that lead to pressure-induced bandgap narrowing. These findings highlight the important role of soft spacer cations in the pressure-tuned optoelectronic properties and provide guidance to the design of new 2D HOIPs.

Multiple responses of 1,6-diphenyl-1,3,5-hexatriene to mechanical stimulation: emission enhancement, piezochromism and negative linear compressibility.

The properties of mechanoresponsive materials are mainly affected by intermolecular interaction, in which anisotropic grinding and hydrostatic high-pressure compression are the powerful tools used for modulation. Upon applying high pressure to 1,6-diphenyl-1,3,5-hexatriene (DPH), the reduced molecular symmetry results in the originally forbidden S0 → S1 transition to become allowed that then leads to a 13-times emission enhancement, and π-π interactions result in piezochromism (red-shifted up to 100 nm). With increasing pressure, high-pressure-stiffened H⋯C/C⋯H and H⋯H interactions enable the DPH molecules to generate a NLC mechanical response (9-15 GPa) with Kb = -5.8764 TPa-1 along the b-axis. As a contrast, upon destroying the intermolecular interactions by grinding, the DPH luminescence blue-shifts from cyan to blue. Based on this research, we investigate a new pressure-induced emission enhancement (PIEE) mechanism and enabled NLC phenomena by controlling weak intermolecular interactions. In-depth research of the evolution of intermolecular interactions has important reference value for developing new fluorescence materials and structural materials.