Space Group P2 Research Articles

Synthesis, crystal structure and antibacterial activity of zinc(II) complexes with Schiff bases derived from 5-fluorosalicylaldehyde

By a condensation of aliphatic amine containing adamantyl groups (amantadine, memantine, or 3-amino-1-adamantanol) and 5-fluorosalicylaldehyde, three new Schiff base ligands, HL1 – 3 , were synthesized. One Schiff base, zinc(II) chloride, and NaOH were stirred in anhydrous methanol generating three new zinc(II) complexes, C34H38F2N2O2Zn (1), C38H46F2N2O2Zn (2), and C34H38F2N2O4Zn (3), respectively. These complexes were characterized by melting point, elemental analysis, infrared spectrum, ultraviolet–visible spectrum, 1H NMR analysis, thermal analysis, and single-crystal X-ray diffraction analysis. Single-crystal X-ray diffraction analysis shows that 1 and 3 crystallize in the monoclinic system with space group P2 1 /c, but 2 crystallizes in the orthorhombic system with space group Pbca. Each asymmetric unit in 1 is composed of one zinc(II) and two deprotonated ligands; each asymmetric unit in 2 is constituted of one zinc(II), two deprotonated ligands as well as one dichloromethane. Each asymmetric unit in 3 is made up of one zinc(II), two deprotonated ligands, one methanol, and one lattice water. The central zinc(II) in 1–3 is four-coordinate via two nitrogen atoms and two oxygen atoms from the corresponding Schiff base ligands, forming a distorted tetrahedral geometry. The antibacterial activities of the three Schiff base ligands and the corresponding complexes against two gram positive bacteria, Staphylococcus aureus and Bacillus subtilis, and a gram negative bacteria, Escherichia coli, were tested.

Guest molecular guided syntheses of 2-dimensional uranyl complexes with rigid benzenedicarboxylate ligands

Two new heterometallic uranyl-organic frameworks (UOFs), [Cd(phen)2(H2O)2][(UO2)2(BDC)3]·2H2O (1) and [Ni(phen)3][(UO2)2(BDC)3]·2H2O (2), were obtained under hydrothermal conditions. Both crystal structures were characterized by single-crystal X-ray diffraction analyses and the results indicate that both complexes feature a similar 2D honeycomb framework that is connected by rigid benzenedicarboxylate (BDC) ligands and uranyl units. BDC works as a linker to bridge neighboring UO2 2+ units, where UO2 2+ is tris-chelated. Different guest molecules guided the stacking of 2D layers and lead into their 3D supramolecular crystal structures with different space groups. As a result, 1 crystallized in a polar space group Cc, whereas 2 belongs to a chiral space group P6122. Thermogravimetric measurements were performed to study their thermal stability. UV-visible diffuse reflectance spectroscopy measurements indicate an experimental optical bandgap of 3.87 eV and 3.63 eV, respectively, for 1 and 2. Luminescent studies of both samples show strong green light emissions.

K2CdGe3S8: A New Infrared Nonlinear Optical Sulfide

A quaternary metal chalcogenide, namely K2CdGe3S8 (I), is obtained through a high-temperature solid-state approach. Compound I crystallizes with the non-centrosymmetric space group P212121. It features a 2D layer structure with [CdGe3S8] layers consisting of tetrahedral GeS4 and CdS4 units, and counter K+ embedded between the layers. The compound exhibits a powder second-harmonic generation (SHG) response of ~0.1 times that of KH2PO4 (KDP) with phase-matchable character at the laser wavelength of 1064 nm. Remarkably, it has a wide band gap (3.20 eV), which corresponds to a favorable high laser-induced damage threshold of 6.7 times that of AgGaS2. In addition, the calculated birefringence (Δn) is 0.039 at the wavelength of 1064 nm, which satisfies the Δn criteria for a promising infrared NLO material.

Preparation, Characterization, DFT Calculations, Antibacterial and Molecular Docking Study of Co(II), Cu(II), and Zn(II) Mixed Ligand Complexes

In the present work, complexes of cobalt(II), copper(II), and zinc(II), 2-amino-4-methylpyrimidineand, and 2,3-diaminopyridine were successfully prepared and characterized using elemental analysis, UV-visible, and FTIR spectroscopy, as well as magnetic susceptibility measurements, molar conductance, TGA analysis, and X-ray diffraction. From elemental and spectral data, the formulae [M(L1)(L2)Cl2(H2O)] (where L1 = AMPY (2-amino-4-methylpyrimidine) and L2 = DAPY(2,3-diaminopyridine)) and M = Co(II) (2), Cu(II) (2), and Zn(II)) for the metal complexes have been proposed. The geometric structures of the mixed-ligand complexes were found to be octahedral around the metal ions, and the XRD patterns showed monoclinic crystal systems with space group P21. The mode of bonding was pentacoordinate for Cu and hexacoordinate for Zn and Co. Different features may result from the fact that not all molecules have the same electron distribution. For example, Zn and Co have larger electron densities in at least one of the chlorides in the HOMO compared with pentacoordinate Cu, which has a small electron distribution on the chloride. Thermal analysis indicated that all metal complexes are stable up to about 88 °C with thermodynamically favored overlapped chemical reactions. Excellent antibacterial and antifungal activity was shown by the three synthesized forms of the complexes. The Zn(II) complex had a high level of antioxidant activity with a DPPH scavenging of 91.5%, whereas the Cu(II) complex had a low level of antioxidant potential (16.5%). The docking tests also showed that all compounds had good binding energy levels (7.2–7.9 kcal mol−1). For this reason, all molecules can easily fit in the receptor protein’s catalytic sites. However, the Co(II) complex is shown to be more active.

Synthesis, growth, crystal structure analysis, optical characterization, thermal and dielectric studies on 2-amino-5-chloropyridinium phenoxyacetate (2A5CPA): An efficient new organic single crystal for nonlinear optical applications

The new organic 2-amino-5-chloropyridinium phenoxyacetate (2A5CPA) nonlinear optical (NLO) crystal was synthesized and grown from methanol solvent by slow evaporation method successfully. The complete 2A5CPA crystal structure was solved by single crystal XRD analysis and it indicates that the 2A5CPA crystal belongs to the tetragonal crystal system with the space group P41212. From the structure, the possible hydrogen bonding interactions have been analyzed. The presence of distinctive functional peaks in the 2A5CPA crystal was affirmed by FTIR analysis. The optical investigation reveals that the crystal was completely transparent in the UV–Vis–NIR region. The TG-DTA investigation assured that the 2A5CPA compound is thermally stable up to 134°C without any decomposition. The sharp endo thermic peak at 205°C in the DTA trace indicates the melting point of the crystal. The broad emissive band at 382[Formula: see text]nm implies the violet emission characteristics of the 2A5CPA crystal. The dielectric study of the 2A5CPA crystal portrays the normal behavior to that of optical materials. The high work-hardening coefficient of 2.94 indicates the soft material nature of the crystal. The LDT value of the 2A5CPA crystal is estimated as 0.6135[Formula: see text]GW/cm2. The third-order NLO properties of the 2A5CPA crystal were analyzed through Z-Scan experiment.

(S)-2-[(S)-2,2,2-Tri-fluoro-1-hy-droxy-eth-yl]-1-tetra-lone.

The crystal structure of the title compound, C12H11F3O2, was elucidated by low-temperature single-crystal X-ray diffraction. The enanti-opure compound crystallizes in the Sohncke space group P21 and features one mol-ecule in the asymmetric unit. The structure displays inter-molecular O-H⋯O hydrogen bonding, which links the mol-ecules into infinite chains propagating parallel to [010]. The absolute configuration was established from anomalous dispersion.

Three-Dimensional Perovskite Phase Transition Materials with Switchable Second Harmonic Generation Properties Introduced by Homochiral (1S,4S)-2,5-Diazabicyclo[2.2.1]-heptane.

Switchable second harmonic generation (SHG) materials have potential applications in information storage, signal processing, and so on because they can switch between SHG-on and SHG-off states. In this work, we designed and synthesized three organic-inorganic hybrid Rb halide three-dimensional (3D) perovskite materials [1S,4S 2,5-2.2.1-H2dabch]RbX3·0.5H2O (X = Cl, 1; Br, 2; I, 3) based on the chiral 1S,4S-2,5-diazabicyclo[2.2.1]heptane (1S,4S-2,5-2.2.1-dabch). The selection of homochiral organic cations ensures that the compounds 1∼3 crystallize in the noncentrosymmetric and chiral space group P212121, which further leads to reversible SHG responses of the three compounds. Through differential scanning calorimetry (DSC) and dielectric measurements, it revealed that the phase transition point of the compounds 1∼3 increased with RbCl, RbBr, and RbI. This is because the hydrogen interaction H···X between the inorganic framework [RbX3]n and the organic cation [1S,4S-2,5-2.2.1-H2dabch]2+ is increased with the order of I > Br > Cl. This study can provide an effective molecular design strategy for the exploration and construction of temperature-tunable SHG switching materials.

L-Cysteine nitrates

The formation of salts in the l-cysteine–HNO3–H2O system was studied yielding three representatives as single crystals: anhydrous l-cysteinium nitrate (l-CysH)NO3 (I) and two new salts (l-CysH···l-Cys)NO3 (II) and (l-CysH···l-Cys)NO3∙0.5H2O (III) with the dimeric (l-CysH···l-Cys) cation. (I), (II) and (III) crystallize in space groups P212121, P21 and I2, respectively. Dimeric cations in (II) and (III) were formed by very short O–H···O hydrogen bonds with R(O···O) distances of 2.440(2) Å and 2.4352(17) Å, respectively. Infrared and Raman spectra of (I-III) were registered and discussed in relation to crystal structures. Characteristics of dimeric cations are compared with those in the previously obtained compounds of l-CysH(l-CysH···l-Cys)F(F···HF), (l-CysH···l-Cys)Cl, (l-CysH···l-Cys)Br and (l-CysH···l-Cys)I·0.5H2O.

Molecular structure of 1,1',6,6'-tetraaza-7,7'-bi(bicyclo[4.1.0]heptane) in gas, solid and solution phases: GED, XRD and NMR data combined with quantum chemical calculations

The equilibrium molecular structure of 1,1',6,6'-tetraaza-7,7'-bi(bicyclo[4.1.0]heptane) in the gas phase has been determined from the data of the gas phase electron diffraction method using quantum chemical calculations up to the RI-MP2/def2-QZVPP level of theory. Structure studies were also carried out in CDCl3 solution using 1D and 2D 1H and 13C NMR spectroscopy and in the solid state using X-ray diffraction analysis. In the gas phase, three conformers of the molecule have been identified, while only one conformer is present in the CDCl3 solution and in the solid state, in which the substance crystallizes in space group P1¯.

Electronic, elastic and pressure-induced phase transitions of tetragonal NaBH4 under high pressure

In this study; the structural, electronic and mechanical properties of sodium borohydride (NaBH4) compound were studied under high hydrostatic pressure from 0 to 300 GPa using the generalized gradient approach (GGA) within the framework of density functional theory (DFT). In the study, the NaBH4 compound transformed from the tetragonal structure with the space group P42 /nmc to the triclinic structure with the space group with the effect of gradually increasing pressure. Enthalpy and total energy calculations were performed to observe the agreement of the study with the experimental results. As a result of the calculations, it was concluded that a phase transition of the NaBH4 compound occurred at approximately 22.6 GPa from the tetragonal structure to the triclinic structure. In addition, the electronic properties of the NaBH4 compound were investigated and 6.22 and 4.95 eV band gaps were obtained for the P42 /nmc and phases, respectively.

Betzite, Na6Ca2(Al6Si6O24)Cl4, a New Cancrinite-Group Mineral from the Eifel Paleovolcanic Region, Germany

AbstractBetzite, ideally Na6Ca2(Al6Si6O24)Cl4, a new cancrinite-group mineral, was discovered in a metasomatically altered (pyrometamorphosed) calcic xenolith, hosted by alkaline basalt at the Bellerberg paleovolcano in the Eastern Eifel region, Rhineland-Palatinate, Germany. The associated minerals are anorthite, phlogopite, diopside, grossular, fluorite, calcite, a tobermorite-like mineral, and vanadoallanite-(Ce). Betzite occurs as colorless hexagonal prismatic crystals up to 2 mm long and up to 0.5 mm thick. The new mineral is brittle, with a Mohs' hardness of 5½. Distinct cleavage on {100} and parting on {0001} are observed. The Dmeas = 2.38(2) g/cm3 and Dcalc = 2.363 g/cm3. Betzite is optically uniaxial (+) with ω = 1.528(2) and ε = 1.545(3). The IR spectrum is given. The chemical composition of betzite is (wt.%; electron microprobe, H2O determined by the modified Penfield method): Na2O 11.88, K2O 4.82, CaO 10.74, MgO 0.21, Al2O3 27.32, Fe2O3 0.68, SiO2 32.84, SO3 1.89, Cl 10.48, H2O 1.10, −O≡Cl −2.37, total 99.59. The empirical formula is Na4.22K1.13Ca2.11Mg0.06(Si6.01Al5.90Fe3+0.09O24)Cl3.25(SO4)0.26(H1.34O0.64). The crystal structure was determined using single-crystal X-ray diffraction data. It is hexagonal, space group P63, a = 12.8166(9) Å, c = 5.3562(3) Å, V = 761.95(12) Å3 (at a temperature of 100 K) and Z = 3. Betzite is a dimorph of quadridavyne, with a disordered distribution of extra-framework components occupying channels. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 11.14 (31) (100), 4.833 (93) (101), 3.715 (95) (300), 3.313 (100) (211), 2.787 (37) (400), 2.681 (56) (002, 131), 2.474 (35) (112, 401), 2.146 (24) (330). The mineral is named in honor of the German amateur mineralogist Volker Betz (b. 1947).

An insight into the hydrogen bonding, halogen bonding and chalcogen bonding interactions in manganese(iii) complexes with N2O2donor salicylidine Schiff base ligands.

Four manganese(iii) complexes, [MnL1(H2O)2]ClO4·H2O (1), [MnL2(H2O)2]ClO4 (2), [MnL3(DMSO)(H2O)]ClO4 (3) and [MnL4(DMSO)(H2O)]ClO4 (4), where H2L1 = N,N'-bis(5-bromosalicylidene)-1,3-diaminopropane, H2L2 = 2,2-dimethyl-N,N-bis(3-methyloxysalicylidene)-1,3-diaminopropane, H2L3 = N,N'-bis(5-chlorosalicylidene)-2,2-dimethyl-1,3-diaminopropane and H2L4 = 2-hydroxy-N,N'-bis(3-ethyloxysalicylidene)-1,3-diaminopropane are tetradentate N2O2-donor ligands and DMSO = dimethyl sulfoxide, have been synthesized and characterised by elemental analysis, IR and UV-vis spectroscopy and single-crystal X-ray diffraction studies. All are monomeric complexes. Complex 1 crystallises in orthorhombic space group P212121, complex 3 crystallises in triclinic space group P-1, whereas complexes 2 and 4 crystallize in monoclinic space groups, C2/c and C2/m respectively. In all the complexes, manganese(iii) has a six-coordinated pseudo-octahedral geometry in which imine nitrogen atoms and phenolate oxygen atoms of the deprotonated di-Schiff base constitute the equatorial plane. In complexes 1 and 2, water molecules are present in the fifth and sixth coordination sites in the axial positions while in complexes 3 and 4 they are occupied by one water and one DMSO. The coordinated water molecules initiate hydrogen-bonded networks in all complexes. DFT calculations have been carried out to analyze two aspects of these complexes viz. the formation of halogen (HaB) and chalcogen bonding (ChB) interactions in complexes 1 and 3 where the electron donor is the perchlorate anion and the acceptor either bromine or chlorine atoms for the HaBs and the sulfur atom of the coordinated DMSO for the ChB. In addition, other intermolecular effects are discussed in the solid state for complexes 1, 2 and 4, where the hydrogen atoms of the coordinated water molecules interact with the electron rich cavities formed by the phenolate and alkyloxy oxygen atoms of the Schiff-base ligand.

A new series of magnetic and luminescent layered hybrid materials obtained from thianthrene phosphonic acid: M(H2O)PO3-S2C12H7 (M = Cu, Zn) and M(H2O)2(PO2OH-S2C12H7)2 (M = Mn, Co).

Four new metallophosphonates with the chemical formulae M(H2O)PO3-S2C12H7 (M = Cu, Zn) and M(H2O)2(PO2OH-S2C12H7)2 (M = Mn, Co) were synthesized using a hydrothermal route from the original bent rigid thianthrene-2-ylphosphonic acid (TPA). This organic precursor crystallizes in a non-centrosymmetric space group P212121 and presents a unique bent geometry due to the presence of two sulfur atoms in its rigid platform architecture. Obtained as single crystal and polycrystalline powders, the structures of the four hybrid materials were solved using X-ray diffraction on single crystals in a monoclinic P21/c space group. These compounds adopt a lamellar structure consisting of one inorganic subnetwork alternating with a 'sawtooth' double organic -S2C12H7 subnetwork. The inorganic layers of these compounds are made of (PO3C) or partially deprotonated (PO2OHC) tetrahedra connected by the apices to isolated ZnO3(H2O) tetrahedra, Cu2O6(H2O)2 copper dimers and cobalt and manganese MO4(H2O)2 octahedra, where the latter two exhibit an isotype structure. Thermogravimetric analysis was performed to confirm the amount of water molecules present in the formula, to track the dehydration process of the structures, and to evaluate their thermal stability. The magnetic properties of the copper, cobalt, and manganese-based materials were investigated from 2 K to 300 K by using a SQUID magnetometer revealing dominant antiferromagnetic interactions with Weiss temperatures of -8.0, -10, and -1 K, respectively. These magnetic behaviors were further corroborated by first-principles simulations based on Density Functional Theory (DFT). Finally, the absorption and photoluminescence properties of both the ligand and hybrid materials were investigated, revealing diverse excitation and recombination mechanisms. The organic moiety based on thianthrene significantly influenced the absorption and emission, with additional peaks attributed to transition metals. Singlet and triplet states recombination were observed, accompanied by an unidentified quenching mechanism affecting the triplet state lifetime.

Second harmonic generation from symmetry breaking stimulated by mixed organic cations in zero-dimensional hybrid metal halides.

Mixing cations with different chemical properties to induce the generation of asymmetric structures is a new approach for tuning the optical properties of hybrid organic-inorganic metal halides (HOIMHs). In this study, zero-dimensional (C9N3H15)(C9H13SO)MBr6 (M = Bi/Sb, [C9N3H15]2+ = [(C4N2H10)(C5NH5)]2+ and [C9H14SO]+ = [CH3(C6H4)OS(CH3)2]+) are synthesized. Two different cations cause both compounds to crystallize in the polar space group P212121, thus resulting in significant phase matchable second harmonic generation under a 1064 nm laser excitation. Thus, (C9N3H15)(C9H13SO)BiBr6 and (C9N3H15)(C9H13SO)SbBr6 exhibit intensities that are approximately 1.8 and 1.7 times that of KH2PO4, respectively. The results of density functional theory calculations show that both (C9N3H15)(C9H13SO)BiBr6 and (C9N3H15)(C9H13SO)SbBr6 exhibit direct bandgaps of 2.95 and 2.81 eV, respectively. Additionally, because of the distortion of the inorganic octahedra, (C9N3H15)(C9H13SO)SbBr6 exhibited bright yellow emission at room temperature, which is attributed to ns2 fluorescence emission. We believe that the symmetry of the HOIMH crystal structure can be broken by introducing spatially differentiated bifunctional organic cations, which consequently enables even-order nonlinear activities.

Retgersite from mine dump of the Lill shaft, Březové Hory ore district, Příbram (Czech Republic)

Rare sulphate of nickel, retgersite, was identified on the one specimen collected on the dump of the Lill shaft, Březové Hory ore district, Příbram (Czech Republic) in 1990s. The specimen consists of quartz gangue with dominant millerite and sphalerite. Retgersite forms light blue to blue-green curved fibrous microcrystalline aggregates up to 2 mm in size with vitreous lustre, growing on the surface and in small outer vugs of the supergene altered gangue. Retgersite was identified by PXRD and its refined unit-cell parameters (for the tetragonal space group P41212) are: a 6.7838(2) Å, c 18.2951(8) Å and V 841.94(4) Å3. Results of semiquantitative chemical analysis (EDS) as well as vibrational spectra (Raman, infrared) including their tentative assignments are also given. The studied retgersite was formed by (sub)recent weathering of primary nickel mineralisation (mostly millerite) in the mine dump conditions.

Three new MnII-[MoIII(CN)7]4- molecular magnets constructed from chiral bidentate chelating ligands.

Three new cyanide-bridged compounds {[Mn((S,S)-Dpen)]3[Mn((S,S)-Dpen)(H2O)][Mo(CN)7]2·4H2O·4C2H3N}n (1-SS), {[Mn((R,R)-Dpen)]3[Mn((R,R)-Dpen)(H2O)][Mo(CN)7]2·4.5H2O·4C2H3N}n (1-RR), and {[Mn(Chxn)][Mn(Chxn)(H2O)0.8][Mo(CN)7]·H2O·4C2H3N}n (2) (SS/RR-Dpen = (S,S)/(R,R)-1,2-diphenylethylenediamine and Chxn = 1,2-cyclohexanediamine) have been successfully synthesized from the self-assembly reaction of the [MoIII(CN)7]4- unit, the MnII ions, and two chiral bidentate chelating ligands. Single-crystal structure determinations show that compounds 1-SS and 1-RR containing ligands SS/RR-Dpen are enantiomers and crystallize in the chiral space group P21. On the other hand, compound 2 crystallizes in the achiral centrosymmetric space group P1̄ due to the racemization of the SS/RR-Chxn ligands during the growth of the crystals. Despite their different space groups and ligands, all three compounds exhibit similar framework structures consisting of cyano-bridged MnII-MoIII two-dimensional layers separated by the bidentate ligands. The circular dichroism (CD) spectra have further demonstrated the enantiopure character of compounds 1-SS and 1-RR. Magnetic measurements revealed that all three compounds display ferrimagnetic ordering with similar critical temperatures of about 40 K. The chiral enantiomers 1-SS and 1-RR exhibit the magnetic hysteresis loop with a coercive field of about 8000 Oe at 2 K, which is by far the highest for all known MnII-[MoIII(CN)7]4- magnets. Analyses of their structures and magnetic properties indicated that their magnetic properties depend on the anisotropic magnetic interactions between the MnII and MoIII centers, which are closely related to the C-N-M bond angles.

Crystal structures of anhydrous borax α-Na<sub>2</sub>B<sub>4</sub>O<sub>7</sub> and γ-Na<sub>2</sub>B<sub>4</sub>O<sub>7</sub> and ab initio quantum chemical calculations of structural stability on their fundamental building blocks

The crystal structures of α-Na2B4O7 and γ-Na2B4O7 formed during the heating of borax were investigated by single-crystal X-ray diffraction. In addition, the structural stability of the fundamental building blocks (FBBs) was examined using ab initio quantum chemical calculations. α-Na2B4O7 crystallized into the triclinic space group P1 with unit cell dimensions of a = 6.5489(7) Å, b = 8.6261(9) Å, c = 10.4909(11) Å, α = 93.2540(10)°, β = 94.8660(10)°, γ = 90.8380(10)°, V = 589.45(11) Å3. γ-Na2B4O7 crystallized into the triclinic space group P1 with unit cell dimensions of a = 6.7123(11) Å, b = 9.6052(17) Å, c = 13.270(2) Å, α = 104.183(4)°, β = 91.560(4)°, γ = 106.501(4)°, and V = 791.0(2) Å3. In both α-Na2B4O7 and γ-Na2B4O7, Na coordination polyhedra with the same coordination numbers have similar coordination volumes; however, the Na polyhedra in γ-Na2B4O7 possess more distortable environments than those in α-Na2B4O7. The flexibility of the Na coordination environment allows these materials to adopt favorable oxygen positions, leading to an α-γ phase transition. The structural stability of the FBBs in α-Na2B4O7 and γ-Na2B4O7 was lowered by dehydration and recrystallization. Consequently, α-Na2B4O7 and γ-Na2B4O7 possess FBBs with readily changeable connection geometries, which causes a phase transformation between α-Na2B4O7 and γ-Na2B4O7 without requiring a significant amount of energy.

3D-printed polymer composite devices based on a ferroelectric chiral ammonium salt for high-performance piezoelectric energy harvesting.

Three-dimensional printing (3DP) is an emerging technology to fabricate complex architectures, necessary to realize state-of-the-art flexible and wearable electronic devices. In this regard, top-performing devices containing organic ferro- and piezoelectric compounds are desired to circumvent significant shortcomings of conventional piezoceramics, e.g. toxicity and high-temperature device processibility. Herein, we report on a 3D-printed composite of a chiral ferroelectric organic salt {[Me3CCH(Me)NH3][BF4]} (1) with a biodegradable polycaprolactone (PCL) polymer that serves as a highly efficient piezoelectric nanogenerator (PENG). The ferroelectric property of 1 originates from its polar tetragonal space group P42, verified by P-E loop measurements. The ferroelectric domain characteristics of 1 were further probed by piezoresponse force microscopy (PFM), which gave characteristic 'butterfly' and hysteresis loops. The PFM amplitude vs. drive voltage measurements gave a relatively high magnitude of the converse piezoelectric coefficient for 1. PCL polymer composites with various weight percentages (wt%) of 1 were prepared and subjected to piezoelectric energy harvesting tests, which gave a maximum open-circuit voltage of 36.2 V and a power density of 48.1 μW cm-2 for the 10 wt% 1-PCL champion device. Furthermore, a gyroid-shaped 3D-printed 10 wt% 1-PCL composite was fabricated to test its practical utility, which gave an excellent output voltage of 41 V and a power density of 56.8 μW cm-2. These studies promise the potential of simple organic compounds for building PENG devices using advanced manufacturing technologies.

Structure Determination of the Crystalline LiPON Model Structure Li5+x P2 O6-x N1+x with x≈0.9.

Non-crystalline lithium oxonitridophosphate (LiPON) is used as solid electrolyte in all-solid-state batteries. Crystalline lithium oxonitridophosphates are important model structures to retrieve analytical information that can be used to understand amorphous phases better. The new crystalline lithium oxonitridophosphate Li5+x P2 O6-x N1+x was synthesized as an off-white powder by ampoule synthesis at 750-800 °C under Ar atmosphere. It crystallizes in the monoclinic space group P21 /c with a=15.13087(11) Å, b=9.70682(9) Å, c=8.88681(7) Å, and β=106.8653(8)°. Two P(O,N)4 tetrahedra connected by an N atom form the structural motif [P2 O6-x N1+x ](5+x)- . The structure was elucidated from X-ray diffraction data and the model corroborated by NMR and infrared spectroscopy, and elemental analyses. Measurements of ionic conductivity show a total ionic conductivity of 6.8×10-7 S cm-1 at 75 °C with an activation energy of 0.52±0.01 eV.

CONDUCTIVITY OF SOLID FLUORIDE-CONDUC­TING PHASES BaxPb0.86-xSn1.14F4

This work presents the results of research of complex solid fluoride ion conducting phases based on lead and tin fluorides. Structure and conductive properties of solid solutions based on PbSnF4 were investigated. Series of samples were synthesized with replacement of lead cations with barium cations in structure of Pb0.86Sn1.14F4 in the concentration range of 0 ≤x ≤0.86. The barium cation has a larger radius and does not have a stereoactive lone pair of electrons, which can have a significant contribution to the conductivity of the synthesized phases and the characteristics of fluoride ion transportation in them.
 It was established that with partial or complete replacement of lead cations with barium cations in the fluoride ion conducting phases in Pb0.86Sn1.14F4 solid solutions of BaxPb0.86‑xSn1.14F4 , where x takes the values 0 ≤x ≤0.86 are formed. The symmetry of the crystal lattice of the synthesized phases in the concentration range of 0 ≤x ≤0.43 corresponds to the structural type of β-PbSnF4 (space group P4/ nmm). Farther increase in the content of barium fluoride cause their crystal lattice to rearrange and approach the structural type of BaSnF4 with preservation of the space group symmetry. The conductive properties of the synthesized phases were investigated.
 We register increase in conductivity of samples bound to increase of barium cation content in the range of 0 ≤x ≤0.43. After reaching peak in conductivity of samples it gradually lowers with increase of barium cation content in the range of 0.43 ≤x ≤0.86.
 The fluoride ion conducting phase Pb0.43Ba0.43Sn1.14F4, isostructural to β-PbSnF4, in comparison with the currently known fluoride-conducting phases has have the highest electrical conductivity in a wide temperature range. Its conductivity is almost two orders of magnitude higher than that of β-PbSnF4 and is 0.12 S/cm at 373 K. With 19FNMR method, it was determined that electrical conductivity is mainly provided by internodal fluorine anions, which are localized between layers of barium and stanium cations. The transfer numbers for fluorine anions in the synthesized phases correspond to the theoretical ones.