Synthesis, the Reversible Isostructural Phase Transition, and the Dielectric Properties of a Functional Material Based on an Aminobenzimidazole-Iron Thiocyanate Complex.

By introducing disordered molecules into a crystal structure, the motion of the disordered molecules easily induces the formation of multidimensional frameworks in functional crystal materials, allowing for structural phase transitions and the realization of various dielectric properties within a certain temperature range. Here, we prepared a novel ionic complex [C7H8N3]3[Fe(NCS)6]·H2O (1) between 2-aminobenzimidazole and ferric isothiocyanate from ferric chloride hexahydrate, ammonium thiocyanate, and 2-aminobenzimidazole using the evaporation of the solvent method. The main components, the single-crystal structure, and the thermal and dielectric properties of the complex were characterized using infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder XRD, thermogravimetric analysis, differential scanning calorimetry, variable-temperature and variable-frequency dielectric constant tests, etc. The analysis results indicated that compound 1 belongs to the P21/n space group. Within the crystal structure, the [Fe(NCS)6]3- anion formed a two-dimensional hydrogen-bonded network with the organic cation through S···S interactions and hydrogen bonding. The disorder-order motion of the anions and cations within the crystal and the deformation of the crystal frameworks lead to a significant reversible isostructural phase transition and multiaxial dielectric anomalies of compound 1 at approximately 240 K.

Solid-State [2+2] Photoreaction of Isostructural Cd(II) Metal Complexes and Solid-State Fluorescence.

A green method to synthesize cyclobutane derivatives has been developed over the past three decades in the form of solid-state [2+2] photochemical reactions. These solid-state reactions also play a major role in the structural transformation of hybrid materials. In this regard, crystal engineering has played a major role in designing photoreactive molecular systems. Here, we report three novel binuclear Cd(II) complexes with the molecular formula [Cd2(4spy)4L4], where 4spy = 4-styryl pyridine and L = p-toluate (1); 4-fluorobenzoate (2); and 3-fluorobenzoate (3). Although three different benzoates are used, all three complexes are isostructural, as corroborated through SCXRD experiments. Structural analysis also helped in identifying two potential photoreactions. These are both intra- and intermolecular in nature and are driven by the head-to-head (HH) and head-to-tail (HT) alignment of 4spy linkers within these metal complexes. 1H NMR spectroscopy studies showed evidence of a quantitative head-to-head photoreaction in all these three complexes, and SCXRD analysis of the recrystallization of the photoproducts also provided confirmation. TGA studies of these photoreactive complexes showed an increase in the thermal stability of the complexes due to the solid-state photoreaction. Photoluminescence studies of these complexes have been conducted, showing a blue shift in emission spectra across all three cases after the photoreaction.

Isostructural Synthesis of Iron-Based Prussian Blue Analogs for Sodium-Ion Batteries.

Rechargeable sodium ion batteries (SIBs) have promising applications in large-scale energy storage systems. Iron-based Prussian blue analogs (PBAs) are considered as potential cathodes owing to their rigid open framework, low-cost, and simple synthesis. However, it is still a challenge to increase the sodium content in the structure of PBAs and thus suppress the generation of defects in the structure. Herein, a series of isostructural PBAs samples are synthesized and the isostructural evolution of PBAs from cubic to monoclinic after modifying the conditions is witnessed. Accompanied by, the increased sodium content and crystallinity are discovered in PBAs structure. The as-obtained sodium iron hexacyanoferrate (Na1.75 Fe[Fe(CN)6 ]0.9743 ·2.76H2 O) exhibits high charge capacity of 150 mAh g-1 at 0.1 C (17 mA g-1 ) and excellent rate performance (74 mAh g-1 at 50 C (8500 mA g-1 )). Moreover, their highly reversible Na+ ions intercalation/de-intercalation mechanism is verified by in situ Raman and Powder X-ray diffraction (PXRD) techniques. More importantly, the Na1.75 Fe[Fe(CN)6 ]0.9743 ·2.76H2 O sample can be directly assembled in a full cell with hard carbon (HC) anode and shows excellent electrochemical performances. Finally, the relationship between PBAs structure and electrochemical performance is summarized and prospected.

Pseudocapacitive Properties of Isostructural Oxides Sr2 LaBMnO7 (B=Co, Fe).

Pseudocapacitors promise to fill the gap between traditional capacitors and batteries by delivering reasonable energy densities and power densities. In this work, pseudocapacitive charge storage properties are demonstrated for two isostructural oxides, Sr2 LaFeMnO7 and Sr2 LaCoMnO7 . These materials comprise spatially separated bilayer stacks of corner sharing BO6 units (B=Fe, Co or Mn). The spaces between stacks accommodate the lanthanum and strontium ions, and the remaining empty spaces are available for oxide ion intercalation, leading to pseudocapacitive charge storage. Iodometric titrations indicate that these materials do not have oxygen-vacancies. Therefore, the oxide ion intercalation becomes possible due to their structural features and the availability of interstitial sites between the octahedral stacks. Electrochemical studies reveal that both materials show promising energy density and power density values. Further experiments through fabrication of a symmetric two-electrode cell indicate that these materials retain their pseudocapacitive performance over hundreds of galvanostatic charge-discharge cycles, with little degradation even after 1000 cycles.

In situ synthesis of multivariant zeolitic tetrazolate imidazole frameworks (ZTIFs) with uncoordinated N-heteroatom sites for efficient adsorption of antiviral drugs.

The current outbreak of the coronavirus (COVID-19) pandemic has significantly increased the global usage of antiviral drugs (AVDs), leading to higher concentrations of antibiotics in water pollution. To address this current issue, a new kind of adsorbent named isostructural zeolitic tetrazolate imidazolate frameworks (ZTIFs) were synthesized by combining imidazole and tetrazolates into one self-assembly approach by adjusting pores and stability of frameworks. The incorporation of imidazole ligand progressively increased the stability of frameworks. Furthermore, increasing the content of tetrazolate ligand greatly improved the adsorption performance due to N-rich sites by increasing the pore size. The obtained adsorbent composite exhibits macroporous structure up to 53.05 nm with excellent structural stability. Owing to their macropores and highly exposed active sites, the synthesized ZTIFs exhibit the maximum adsorption capacity for oseltamivir (OT) and ritonavir (RT) of 585.2 mg/g and 435.8 mg/g, respectively. Moreover, the adsorption uptake and saturation process were rapid compared to simple MOF. Within 20 min, both pollutants achieved equilibrium. The adsorption isotherms were best interpreted by Pseudo second order kinetics. The adsorption of AVDs on ZTIFs was spontaneous, exothermic, and thermodynamically feasible. The DFT calculations and characterization results after adsorption demonstrate that π-π interaction, pore filling, surface complexation, and electrostatic interaction were the primary features of the adsorption mechanism. The prepared ZTIFs composite exhibits high chemical, mechanical and thermal stability and can be recycled multiple times without destroying its morphology and structure. The adsorbent regeneration for several cycles impacted the operational cost and the eco-friendly characteristic of the process.

Lone Pair π Contacts and Structure Signatures of r(UNCG) Tetraloops, Z-Turns, and Z-Steps: A WebFR3D Survey.

Z-DNA and Z-RNA have long appeared as oddities to nucleic acid scientists. However, their Z-step constituents are recurrently observed in all types of nucleic acid systems including ribosomes. Z-steps are NpN steps that are isostructural to Z-DNA CpG steps. Among their structural features, Z-steps are characterized by the presence of a lone pair…π contact that involves the stacking of the ribose O4' atom of the first nucleotide with the 3'-face of the second nucleotide. Recently, it has been documented that the CpG step of the ubiquitous r(UNCG) tetraloops is a Z-step. Accordingly, such r(UNCG) conformations were called Z-turns. It has also been recognized that an r(GAAA) tetraloop in appropriate conditions can shapeshift to an unusual Z-turn conformation embedding an ApA Z-step. In this report, we explore the multiplicity of RNA motifs based on Z-steps by using the WebFR3D tool to which we added functionalities to be able to retrieve motifs containing lone pair…π contacts. Many examples that underscore the diversity and universality of these motifs are provided as well as tutorial guidance on using WebFR3D. In addition, this study provides an extensive survey of crystallographic, cryo-EM, NMR, and molecular dynamics studies on r(UNCG) tetraloops with a critical view on how to conduct database searches and exploit their results.

Stabilization of Near Identical Hydrogen Bonded Octameric Water Clusters in Crystal Structures of Three Distinct Non-Charged Polyamide Macrocyclic Host Molecules.

In this paper, we present a comparative analysis of the solid state structures of three well-resolved hydrates of macrocyclic host molecules 1a, 1b, and 2 containing an intrannular amide-aryl substituent (lariat arm) connected to a fixed 26-membered ring in a normal (-NHCOAr, hosts 1a and 1b) or reverse manner (-CONHAr, host 2). Despite different chemical structures, these hosts crystallize as isostructural tetrahydrates in the same P-1 space group. Moreover, their crystals exhibit identical hydrogen bond motifs resulting in a stabilization of an almost identical unusual octameric water cluster built from the cyclic tetramer core and four water molecules, attached sequentially in an "up-and-down" manner. Further analysis reveals that, among the series, the structure of host 2 provides the most suitable environment for the accommodation of this type of water cluster.

Unusual Mott transition in multiferroic PbCrO3.

The Mott insulator in correlated electron systems arises from classical Coulomb repulsion between carriers to provide a powerful force for electron localization. Turning such an insulator into a metal, the so-called Mott transition, is commonly achieved by "bandwidth" control or "band filling." However, both mechanisms deviate from the original concept of Mott, which attributes such a transition to the screening of Coulomb potential and associated lattice contraction. Here, we report a pressure-induced isostructural Mott transition in cubic perovskite PbCrO3. At the transition pressure of ∼3 GPa, PbCrO3 exhibits significant collapse in both lattice volume and Coulomb potential. Concurrent with the collapse, it transforms from a hybrid multiferroic insulator to a metal. For the first time to our knowledge, these findings validate the scenario conceived by Mott. Close to the Mott criticality at ∼300 K, fluctuations of the lattice and charge give rise to elastic anomalies and Laudau critical behaviors resembling the classic liquid-gas transition. The anomalously large lattice volume and Coulomb potential in the low-pressure insulating phase are largely associated with the ferroelectric distortion, which is substantially suppressed at high pressures, leading to the first-order phase transition without symmetry breaking.

Strain-Induced Isostructural and Magnetic Phase Transitions in Monolayer MoN2.

The change of bonding status, typically occurring only in chemical processes, could dramatically alter the material properties. Here, we show that a tunable breaking and forming of a diatomic bond can be achieved through physical means, i.e., by a moderate biaxial strain, in the newly discovered MoN2 two-dimensional (2D) material. On the basis of first-principles calculations, we predict that as the lattice parameter is increased under strain, there exists an isostructural phase transition at which the N-N distance has a sudden drop, corresponding to the transition from a N-N nonbonding state to a N-N single bond state. Remarkably, the bonding change also induces a magnetic phase transition, during which the magnetic moments transfer from the N(2p) sublattice to the Mo(4d) sublattice; meanwhile, the type of magnetic coupling is changed from ferromagnetic to antiferromagnetic. We provide a physical picture for understanding these striking effects. The discovery is not only of great scientific interest in exploring unusual phase transitions in low-dimensional systems, but it also reveals the great potential of the 2D MoN2 material in the nanoscale mechanical, electronic, and spintronic applications.

Phenyl Groups Result in the Highest Benzene Storage and Most Efficient Desulfurization in a Series of Isostructural Metal-Organic Frameworks.

A series of isoreticular metal-organic frameworks (MOFs; NENU-511-NENU-514), which all have high surface areas and strong adsorption capacities, have been successfully constructed by using mixed ligands. NENU-513 has the highest benzene capacity of 1687 mg g(-1) at 298 K, which ranks as the top MOF material among those reported up to now. This NENU series has been used for adsorptive desulfurization because of its permanent porosity. The results indicate that this series has a higher adsorptive efficiency in the removal of organosulfur compounds than other MOF materials, especially NENU-511, which has the highest adsorptive efficiency in the ambient atmosphere. This study proves that the design and synthesis of targeted MOFs with higher surface areas and with functional groups present is an efficient method to enhance benzene-storage capacity and the adsorption of organosulfur compounds.

Solid-state NMR and computational investigation of solvent molecule arrangement and dynamics in isostructural solvates of droperidol.

(13)C, (15)N and (2)H solid-state NMR spectroscopy have been used to rationalize arrangement and dynamics of solvent molecules in a set of isostructural solvates of droperidol. The solvent molecules are determined to be dynamically disordered in the methanol and ethanol solvates, while they are ordered in the acetonitrile and nitromethane solvates. (2)H NMR spectra of deuterium-labelled samples allowed the characterization of the solvent molecule dynamics in the alcohol solvates and the non-stoichiometric hydrate. The likely motion of the alcohol molecules is rapid libration within a site, plus occasional exchange into an equivalent site related by the inversion symmetry, while the water molecules are more strongly disordered. DFT calculations strongly suggest that the differences in dynamics between the solvates are related to differences in the energetic penalty for reversing the orientation of a solvent molecule.

Rational synthesis of two isostructural thiophene-containing metal-organic frameworks toward photocatalytic degradation of organic pollutants.

In this work, thiophene moieties (as the crucial functional groups) have been successfully incorporated into the skeleton of metal-organic frameworks (MOFs) by using thienyl-substituted triazole ligands. Reaction of AgCF3SO3 with 3-phenyl-5-(2-thienyl)-1,2,4-triazole (PTTzH) or 3,5-bis(2-thienyl)-1,2,4-triazole (BTTzH) afforded two isostructural MOFs (AgTz-3 and AgTz-4) in gram-scale. AgTz-4 with higher thiophene content showed significantly stronger photocatalytic activity than AgTz-3 with lower thiophene content. Noteworthy, the photodegradation rate constants of AgTz-4 were 0.055 mg·L-1·min-1 for rhodamine B and 0.24 min-1 for salazosulfapyridine, which is comparable or even higher than some MOF-based materials reported in the literature. More importantly, AgTz-4 demonstrated good reusability and stability after four cycles of photodegradation. Our experimental results revealed that the enhanced photodegradation efficiency can be attributed to the increased light absorption capacity and optimized band structure of Ag-MOFs resulting from the introduction of thiophene groups into MOF structures.

Iso-structural phase transition in pyrochlore iridates (Sm _{1-x}$Bix)2Ir2O7(x= 0, 0.02, and 0.10): high-pressure Raman and x-ray diffraction studies.

The pyrochlore iridates,A2Ir2O7, show a wide variety of structural, electronic, and magnetic properties controlled by the interplay of different exchange interactions, which can be tuned by external pressure. In this work, we report pressure-induced iso-structural phase transitions at ambient temperature using synchrotron-based x-ray diffraction (up to ∼20 GPa) and Raman-scattering measurements (up to ∼25 GPa) of the pyrochlore series (Sm_{1-x}Bix)2Ir2O7(x= 0, 0.02, and 0.10). Our Raman and x-ray data suggest an iso-structural transition in Sm2Ir2O7atPc∼ 11.2 GPa, associated with the rearrangement of IrO6octahedra in the pyrochlore lattice. The transition pressure decreases to ∼10.2 and 9 GPa forx= 0.02 and 0.10, respectively. For all the samples, the linewidth of three phonons associated with Ir-O-Ir (A1gandEg) and Ir-O (T2g4) vibrations show anomalous decrease up toPc, due to decrease in electron-phonon interaction.

Structural insights into supramolecular interactions in isostructural salts of 2,4,6-triaminopyrimidinium with various heterocyclic carboxylates.

2,4,6-Triaminopyrimidine is an interesting and challenging molecule due to the presence of multiple hydrogen-bond donors and acceptors. Its noncovalent interactions with a variety of carboxylic acids provide several supramolecular aggregates with frequently occurring molecular synthons. The present work focuses on the supramolecular interactions of 2,4,6-triaminopyrimidinium 3-(indol-3-yl)propionate-3-(indol-3-yl)propionic acid (1/1), C4H8N5+·C11H10NO2-·C11H11NO2, (I), 2,4,6-triaminopyrimidinium 2-(indol-3-yl)acetate, C4H8N5+·C10H8NO2-, (II), 2,4,6-triaminopyrimidinium 5-bromothiophene-2-carboxylate, C4H8N5+·C5H2BrO2S-, (III), and 2,4,6-triaminopyrimidinium 5-chlorothiophene-2-carboxylate, C4H8N5+·C5H2ClO2S-, (IV). All four salts exhibit robust homomeric and heteromeric R22(8) ring motifs. Salts (I) and (II) develop sextuple [in (I)] and quadruple [in (I) and (II)] hydrogen-bonded arrays through fused-ring motifs. Salt (II) exhibits a rosette-like architecture. Salt (IV) is isostructural and isomorphous with salt (III), exhibiting an identical crystal structure with a different composition and an identical supramolecular architecture. In salts (III) and (IV), a linear hetero-tetrameric motif is formed and, in addition, both salts exhibit halogen-π interactions which enhance the crystal stability. All four salts develop a supramolecular hydrogen-bonded pattern facilitated by several N-H...O and N-H...N hydrogen bonds with multiple furcated donors and acceptors.

Isostructural behaviour in ammonium and potassium salt forms of sulfonated azo dyes.

The structures of five ammonium salt forms of monosulfonated azo dyes, derivatives of 4-(2-phenyldiazen-1-yl)benzenesulfonate, with the general formula [NH4][O3S(C6H4)NN(C6H3)RR']·XH2O [R = OH, NH2 or N(C2H4OH)2; R' = H or OH] are presented. All form simple layered structures with alternating hydrophobic (organic) and hydrophilic (cation, solvent and polar groups) layers. To assess for isostructural behaviour of the ammonium cation with M+ ions, the packing of these structures is compared with literature examples. To aid this comparison, the corresponding structures of four potassium salt forms of the monosulfonated azo dyes are also presented herein. Of the five ammonium salts it is found that three have isostructural equivalents. In two cases this equivalent is a potassium salt form and in one case it is a rubidium salt form. The isostructurality of ion packing and of unit-cell symmetry and dimensions tolerates cases where the ammonium ions form somewhat different interaction types with coformer species than do the potassium or rubidium ions. No sodium salt forms are found to be isostructural with any ammonium equivalent. However, similarities in the anion packing within a single hydrophobic layer are found for a group that consists of the ammonium and rubidium salt forms of one azo anion species and the sodium and silver salt forms of a different azo species.

Structural studies of various olmesartan solvates.

Seven solvates of the angiotensin II receptor blocker agent olmesartan (C24H26N6O3), namely, the methanol (C24H26N6O3·CH4O), ethanol (C24H26N6O3·C2H6O), isopropanol (C24H26N6O3·C3H8O), isobutanol (C24H26N6O3·C4H10O), 2-ethoxyethanol (C24H26N6O3·C4H10O2), chloroform (C24H26N6O3·CHCl3) and acetonitrile (C24H26N6O3·C2H3N) solvates, were successfully obtained. The crystal structures were determined using the single-crystal X-ray diffraction technique and the structural features are described, each solvate containing one molecule of olmesartan and one of solvent in the asymmetric unit. The samples were also analyzed by powder X-ray diffraction. Total lattice energies and binding energies between the olmesartan and solvent molecules were evaluated, which can be partitioned into electrostatic, polarization, dispersion and repulsion components. Hirshfeld and fingerprint plot analysis was performed to highlight the intermolecular contacts. Hydrogen bonding and supramolecular arrangements were comparatively studied for the seven solvates.

Investigation of crystal structures, energetics and isostructurality in halogen-substituted phosphoramidates.

A total of 14 compounds, one unsubstituted and 13 halogen-substituted phosphoramidates, have been synthesized from unsubstituted and halogenated (fluoro-, difluoro-, chloro-, bromo-, iodo-substituted) aniline and diphenyl phosphoryl chloride to investigate their molecular assembly in solid-state structures. Amongst them, six groups were formed based on similarities in unit-cell dimensions, space group and molecular assembly of the crystal. The analysis reveals that all the crystal structures contain robust N-H...O hydrogen bonds which are the primary building blocks with ancillary interactions such as C-H...O, C-H...π, C-H...F/Cl/Br/I, F...F, F...π, I...π, Br...π, I...O and Br...O. The role of short and directional C-H...O and C-H...π interactions providing significant stabilization to the densely packed crystalline arrangement is discussed. The contribution of these interactions in stabilizing the crystalline assembly was deduced via computing total interaction energy between dimers and the overall lattice energies using the computer programs Crystal Explorer 17.5 and PIXELC, respectively. Additionally, the occurrence of 3D isostructurality in phosphoradimates and their halogenated analogs was investigated using the XPac program. A comparison of the magnitudes of the torsion angles in the compounds substantiates the role of conformational flexibility in the solid state.

Negative linear compressibility in Se at ultra-high pressure above 120 GPa.

A series of in situ synchrotron X-ray diffraction (XRD) measurements were carried out, combined with first-principles calculations, to study structural phase transitions of selenium at high pressures and room temperature. Several phase transitions were observed, among which an isostructural phase transition was found at around 120 GPa for the first time. Evolved from the rhombohedral (space group R 3 m) structure (Se-V), the new phase (Se-V') exhibited an interesting increase of lattice parameter a at pressures from 120 to 148 GPa, known as negative linear compressibility (NLC). The discovery of NLC behavior observed in this work is mainly attributed to the accuracy and fine steps controlled by the membrane system for in situ XRD data collected with an exposure time of 0.5 s. After 140 GPa, a body-centered cubic (b.c.c.) structure Se-VI (space group Im 3 m) was formed, which remains stable up to 210 GPa, the highest pressure achieved in this study. The bulk moduli of phases Se-V, Se-V' and Se-VI were estimated to be 83 ± 2, 321 ± 2 and 266 ± 7 GPa, respectively, according to the P-V curve fit by the third-order Birch-Murnaghan equation of state. The Se-V' phase shows a bulk modulus almost 4 times larger than that of the Se-V phase, which is mainly due to the effect of its NLC. NLC in a higher pressure range is always more significant in terms of fundamental mechanism and new materials discovery, yet it has barely been reported at pressures above 100 GPa. This will hopefully inspire future studies on potential NLC behaviors in other materials at ultra-high pressure.

Competition between chalcogen and halogen bonding assessed through isostructural species.

The amino group of 2-amino-5-(4-halophenyl)-1,3,4-chalcogenadiazole has been replaced with bromo/iodo substituents to obtain a library of four compositionally related compounds. These are 2-iodo-5-(4-iodophenyl)-1,3,4-thiadiazole, C8H4I2N2S, 2-bromo-5-(4-bromophenyl)-1,3,4-selenadiazole, C8H4Br2N2Se, 2-bromo-5-(4-iodophenyl)-1,3,4-selenadiazole, C8H4BrIN2Se, and 2-bromo-5-(4-iodophenyl)-1,3,4-thiadiazole, C8H4BrIN2S. All were isostructural and contained bifurcated Ch...N (Ch is chalcogen) and X...X (X is halogen) interactions forming a zigzag packing motif. The noncovalent Ch...N interaction between the chalcogen-bond donor and the best-acceptor N atom appeared preferentially instead of a possible halogen bond to the same N atom. Hirshfeld surface analysis and energy framework calculations showed that, collectively, a bifurcated chalcogen bond was stronger than halogen bonding and this is more structurally influential in this system.

A new isostructural halogenated chalcone with optical properties.

Chalcones are organic compounds that present a number of properties. This study presents a comprehensive structural description of a new derivative of a chlorine-substituted chalcone in comparison with a bromine chalcone. Also, supermolecule and sum-over-state approach were used to describe the optical properties of these structures regarding the substitution of the bromine by the chlorine atom. In addition, the electrical properties, dipole moment, linear polarizability, and second IDRI hyperpolarizability were calculated. The linear refractive index and the third-order nonlinear macroscopic susceptibility were evaluated as a function of the applied electric field frequency. Furthermore, the quantum mechanics calculations that were implemented at the M06-2X/6-311++G(d,p) level of the theory for these isostructural chalcones indicate that the change in halogen atoms does not cause meaningful changes in their conformation. Finally, we can postulate that side-to-side and the antiparallel interactions are the interaction forces that drive the crystal growth for new isostructural chalcones. The NLO properties showed title compounds that are good candidates for use as NLO materials.