Space Group Pna21 Research Articles

Achiral Au(I) Cyclic Trinuclear Complexes with High-Efficiency Circularly Polarized Near-Infrared TADF.

Realizing high photoluminescence quantum yield (PLQY) in the near-infrared (NIR) region is challenging and valuable for luminescent material, especially for thermally activated delay fluorescence (TADF) material. In this work, we report two achiral cyclic trinuclear Au(I) complexes, Au3 (4-Clpyrazolate)3 and Au3 (4-Brpyrazolate)3 (denoted as Cl-Au and Br-Au), obtained through the reaction of 4-chloro-1H-pyrazole and 4-bromo-1H-pyrazole with Au(I) salts, respectively. Both Cl-Au and Br-Au exhibit TADF with high PLQY (>70 %) in the NIR I (700-900 nm) (λmax = 720 nm) region, exceeding other NIR-TADF emitters in the solid state. Photophysical experiments and theoretical calculations confirmed the efficient NIR-TADF properties of Cl-Au and Br-Au were attributed to the small energy gap ΔE(S1-T2) (S = singlet, T = triplet) and the large spin-orbital coupling induced by ligand-to-metal-metal charge transfer of molecular aggregations. In addition, both complexes crystallize in the achiral Pna21 space group (mm2 point group) and are circularly polarized light (CPL) active with maxima luminescent dissymmetry factor |glum | of 3.4 × 10-3 (Cl-Au) and 2.7 × 10-3 (Br-Au) for their crystalline powder samples, respectively. By using Cl-Au as the emitting ink, 3D-printed luminescent logos are fabricated, which own anti-counterfeiting functions due to its CPL behavior dependent on the crystallinity.

Stibiotantalite from the Nanyangshan LCT Pegmatite, North Qinling Orogen, Central China: Occurrence and New Data on its Crystal Chemistry

ABSTRACT Stibiotantalite, SbTaO4, from the Nanyangshan LCT pegmatite, North Qinling Orogen, Central China is described. The mineral is associated with oxystibiomicrolite, oxycalcioroméite, hydrokenomicrolite, hydroxynatromicrolite, hydromicrolite, stibnite, bismuthinite, tantalite-(Mn), columbite-(Mn), spodumene, polylithionite, trilithionite, luanshiweiite, fluorluanshiweiite, elbaite, albite, and quartz. Results from electron microprobe data analysis (n = 4) yield the average empirical formula (based on O = 4): (Sb0.96Bi0.04)Σ1.00(Ta0.85Nb0.15)Σ1.00O4. The seven strongest X-ray powder diffraction lines are [d in Å (I)(hkl)] 3.126(100)(121), 2.964(81)(040), 5.976(27)(020), 3.515(22)(111), 1.891(22)(240), 1.736(19)(161), and 2.693(16)(131). Single-crystal X-ray diffraction (SXRD) patterns show strong reflections consistent with space group Pna21. The refined unit-cell parameters from the SXRD data are a 5.5419(2) Å, b 4.9200(2) Å, c 11.8003(5) Å, and V 321.75(2) Å3 with Z = 4. The structure has been refined to a final R1 = 0.0173 on the basis of 766 reflections with Fo > 4σ(Fo). In the previous study, the AO6 octahedron of stibiotantalite was close to an ideal octahedron. The new structure refinement of stibiotantalite from the Nanyangshan pegmatite indicates that the AO6 octahedron has a larger distortion due to the lone-pair effect of Sb3+. The high-quality structural data presented in this study gives a more accurate portrayal of the crystal structure of stibiotantalite than provided in the original description of the mineral.

Photoluminescence and electronic structure of α'-Ag8GeS6 crystals

The Ag8GeS6 crystal was synthesized by the direct melting of the elementary Ag, Ge, and S high-purity grade stoichiometric mixture in a sealed quartz ampoule. This argyrodite crystallizes in orthorhombic structure [Pna21 space group (No. 33)] below ≈483 K. The theoretical first-principle calculations of the electronic band structure and density of states of an α'-Ag8GeS6 crystal are estimated by the generalized gradient approximation. The Perdew–Burke–Ernzerhof functional was utilized. All of the calculated parameters correlate well with the known experimental data. Based on the electronic band structure, the effective mass of the electrons and holes was calculated. The anisotropic behavior of electronic band structure is discussed. Temperature and carrier concentration dependence of the Seebeck coefficient is calculated. The temperature behavior of α'-Ag8GeS6 photoluminescence spectra is presented. The emission spectra are studied in the temperature range between 17 and 130 K and laser power excitation between 4 and 512 mW and in the spectral range of 750–1650 nm. Two main emission bands at ≈1.35 and ≈1.57 eV are observed and discussed.

Growth and Structure of Rare-Earth Molybdate Crystals Na0.65La4.35Mo3O15.81±δF0.07±ε

Rare-earth sodium- and fluorine-substituted molybdates with the Na0.65La4.35Mo3O15.81±δF0.07±ε composition were synthesized for the first time as single crystals. An accurate X-ray diffraction analysis of three samples at room temperature showed that the obtained crystals are isostructural to undoped cubic compounds of the Ln5Mo3O16+δ family (space group Pn3¯n). Sodium cations partially occupy one of the two lanthanum positions and center the more distorted LaO8 polyhedra, while fluorine anions occupy over-stoichiometric oxygen positions in the vast interstices (cavities) of the structure. The partial substitution of fluorine atoms for oxygen ones affects the transport characteristics of compounds by activating the oxygen atoms in the anionic subsystem due to the effect of supplementary electrostatic repulsion between anions of different types.

Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates.

The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has intrigued chemists, physicists, and materials scientists for many years. Because the chemical complexity of molecular racemic building units is so varied, targeting these materials is poorly understood. Previously, three isostructural racemic compounds with a formula of [Cu(H2O)(bpy)2]2[MF6]2·2H2O (bpy = 2,2'=bipyridine; M = Ti, Zr, Hf) were shown to crystallize in the NCS space group Pna21, of polar, achiral crystal class mm2. In this work, we synthesized five new racemic compounds with the formula [Cu(H2O)(dmbpy)2]2[MF6]2·xH2O (dmbpy = 4,4'/5,5'-dimethyl-2,2'-bipyridine; M = Ti, Zr, Hf). Single crystal X-ray diffraction reveals that the five newly synthesized compounds feature equimolar combinations of Δ- and Λ-Cu(dmbpy)2(H2O)2+ complexes that are assembled into packing motifs similar to those found in the reported NCS structure but all crystallize in centrosymmetric (CS) space groups. Seven structural descriptors were created to analyze the intermolecular interactions on the assembly of Cu racemates in the CS and NCS structures. The structural analysis reveals that in the CS structures, the inversion center results from parallel heterochiral π-π stacking interactions between adjacent Cu racemates regardless of cation geometries, hydrogen bonding networks, or interlayer architectures, whereas in the NCS structure, nonparallel heterochiral π-π interactions between the adjacent Cu racemates preclude an inversion center. The parallel heterochiral π-π interactions in the CS structures can be rationalized by the restrained geometries of the methyl-substituted ligands. This work demonstrates that the introduction of nonparallel stacking can suppress the formation of an inversion center for an NCS racemate. A conceptual framework and practical approach linking the absence of inversion symmetry in racemates is presented for all NCS crystal classes.

Synthesis and crystal structures of 3-(p-phenylphenyl)-3-hydroxy-N-isopropyl-4,4-dimethylazetidin-2-one and 3-phenyl-3-hydroxy-N-isopropyl-4,4-dimethylazetidin-2-one

Formation of the title compounds 3-(p-phenylphenyl)-3‑hydroxy-N-isopropyl-4,4-dimethylazetidin-2-one, C20H23NO2 (2d), and 3-phenyl-3‑hydroxy-N-isopropyl-4,4-dimethylazetidin-2-one, C14H19NO2 (2a), was achieved by photoreaction of N,N-diisopropyl(p-phenylphenyl)glyoxylamide 1d and N,N-diisopropylphenylglyoxylamide 1a, respectively, in solution and confirmed by nuclear magnetic resonance spectroscopy, infrared spectroscopy, ultraviolet spectroscopy, and single-crystal X-ray diffraction. Compounds 2d and 2a belong to the orthorhombic and monoclinic systems, space groups Pna21 and P21/c, respectively.

Laser-Induced Tunable White Light Emission in Yb3+/Er3+/Tm3+ Ion-Doped La2Ti2O7

A series of compounds with the general formula (La1−xREx)2Ti2O7 (x = 0.005, 0.015, and 0.025) doped with Yb3+, Er3+, and Tm3+ rare Earth ions were prepared by the traditional solid-state reaction at 1350 °C for 24 h. The X-ray powder diffraction technique, high-resolution transmission electron microscopy, and photoluminescence spectroscopy technique were used to characterize the structure and optical properties of the compounds. All compounds showed a single-phase orthorhombic structure with a space group Pna2 1, as confirmed by JCPDS (Cart No: 01-070-1690). The La1.9Yb0.04Er0.01Tm0.05 Ti2O7 nanocrystals exhibited intense tunable white light luminescence signals in the full spectrum, and green and blue emissions were predominant in the Yb3+/Er3+− and Yb3+/Tm3+-doped titanates, respectively. In this study, the influence of concentration and excitation power on the upconversion luminescence, color, and calculated laser-power-induced heating performance of La2Ti2O7 nanophosphors were investigated at room temperature.

Thermal, dielectric, mechanical and structural behavior of 2-amino 4-methylpyridinium 4-nitrophenolate 4-nitrophenol bulk single crystal

Applications in both science and industry have received increased attention as a result of bulk single crystals with particular orientations. However, due to the instability of organic crystals at high temperatures and stress, there is an interest in growing good-quality bulk single crystals with stable thermal and mechanical properties. Here, the 2-amino 4-methylpyridinium 4-nitrophenolate 4-nitrophenol (2A4MPPP) crystal was prepared employing a single-wall ampoule and the vertical Bridgman technique. Structure and functional groups were determined by XRD, NMR, and FTIR studies. More importantly, detailed thermal and kinetic properties such as activation energy, frequency factor, rate constant, and Avrami exponent are discussed. The mechanical stability and dielectric studies are also demonstrated for the title compound. According to the single crystal XRD investigation, 2A4MPPP is a member of the orthorhombic crystal system with the Pna21 space group. Through the TGA and DTA analyses, it was confirmed that the compound starts to melt at 98 °C and complete melting occurs at 103.3 °C. The dielectric experiments reveal the crystal's poor dielectric constant and high-frequency dielectric loss. Vickers microhardness investigations show that grown 2A4MPPP belongs to the soft materials group. As a result of these findings, the 2A4MPPP crystal should be well suited for usage in thermomechanical, microelectronic, optical communications, and nonlinear optical applications.

Rare-Earth Fluorite-like Li0.42La4.58Mo3O15.76±δF0.42±ε Molybdates: Crystal Growth and Atomic Structure

Rare-earth fluorine-containing molybdates of the Ln5Mo3O16+δ oxygen–electron conductor family with the LiLa4Mo3O15F composition were synthesized for the first time as single crystals by the flux method. An accurate X-ray diffraction analysis of the obtained crystals was carried out at 20 and −183 °C. The LiLa4Mo3O15F compound is isostructural to the fluorine-free analogue with a cubic structure (space group Pn3¯n). It is shown that lithium atoms replace one of the two positions of lanthanum in the more distorted LaO8 polyhedron. According to X-ray diffraction analysis, fluorine atoms replace the positions of over-stoichiometric oxygen located in the vast cavities of the structure. So, fluorine anions can promote the interstitial conductivity of F-containing LiLa4Mo3O15F molybdates.

Solving the crystal structure of heterocyclic Poly(arylene benzimidazole) via model compound single crystal and theoretical calculations

Heterocyclic aramid containing benzimidazole units has demonstrated to be one of the strongest fibers. Due to positional isomerism of asymmetric benzimidazole and conformational isomerism of phenylamide, solving the crystal structure of poly(arylene benzimidazole) (PABI) aramid was a prominent challenge. Herein, we first reported the crystal structure of PABI aramid. First, the model compound: N-(4-(5-benzamido-1H-benzo[d] imidazole-2-yl) phenyl) benzamide (PBA) was cultured into single crystal: the molecules took a perfect ross-tenon-mortise interlocking conformation, in which the hydrogen bonding made a giant three-dimensional network. The PABI crystals with PBA crystal stacking feature were subsequently constructed and optimized through theoretical quantum calculation, disclosing a monoclinic unit cell with the parameters (a = 8.56 Å; b = 5.05 Å; and c = 36.78 Å; and β = 91.4°) and Pn space group. Their plausibility and validity were verified, since the simulated XRD and 2D-WAXD patterns reproduced the experimental XRD patterns. Our strategy of linking model compound PBA single crystals to obtain higher PABI crystals, paved the way to solving asymmetrical heterocyclic macromolecules crystals composed of easily isomerized chemical structures.

Possible metal-insulator transition in a bismuth iridium oxide with the KSbO3-type structure

Iridium-based compounds have attracted a lot of attention because of strong spin-orbit coupling in them and resulting exotic magnetic and electronic properties. We report here a high-pressure, high-temperature synthesis (at 6 GPa and 1550 K) of a bismuth iridium oxide with the ideal composition of Bi3Ir3O11. This compound crystallizes in the KSbO3-type structure with space group Pn−3 and the lattice parameter a = 9.39556 Å (at room temperature). The crystal structure was investigated by synchrotron powder X-ray diffraction between 100 K and 800 K. No structural phase transitions or other changes were found up to 600 K; above 600 K, a partial decomposition takes place with the appearance of a small amount of Ir impurity. The structural analysis and density measurements suggested a cation-deficient composition of Bi3−δIr3−δO11 with δ ≈ 0.11. Nearly temperature-independent paramagnetic behavior was observed between 2 K and 400 K. Resistivity measurements showed a rise in resistivity below about 85 K suggesting a possible metal-insulator transition. No magnetoresistence effects were observed.

SINGLE CRYSTALS GROWTH IN THE HOMOGENEITY REGION OF LOW-TEMPERATURE MODIFICATION OF Ag8GeS6

Cationic ion-conductors have found wide practical application as electric batteries. Among them the lithium-ion batteries are the most common commercially used. However, research is being actively carried out to improve the safety of these batteries. Among the possible compounds, silver-containing phases are attractive, since silver-ions, along with high values of ionic conductivity in solid-state, haven’t high chemical activity like the same alkali metal-ions. Realization of the crystal structure necessary for effective ion transport is observed in compounds of the argyrodite structure - a group of ternary chalcogenides and quaternary chalcohalogenides of multi-charged cations (Ge4+, Si4+, P5+). In this work, a study of heterovalent cationic P5+→Ge4+ substitution in the Ag8GeS6 enriched region was carried out. Single crystals of Ag8-x(Ge1-xPx)S6 (x = 0.25; 0.5) solid solutions were grown by the method of directional crystallization using a solution-melt technique. The grown single crystals are characterized by the absence of macrodefects, a dark gray color with a metallic luster, and dimensions of l = ~3 cm and d = 1.2 cm. Using the Rietveld refinement method, the crystal structure was established and the lattice parameters of Ag8-x(Ge1-xPx)S6 (x = 0.25; 0.5) solid solutions were determined. Established, that single crystals of Ag8-x(Ge1-xPx)S6 (x = 0.25; 0.5) solid solutions crystallize in the orthorhombic crystal system in a primitive cell with space group Pna21.
 Keywords: argyrodites; single crystals; directional crystallization; phase analysis.

Interplay between Fe(II) and Fe(III) and Its Impact on Thermoelectric Properties of Iron-Substituted Colusites Cu26−xFexV2Sn6S32

Following the trend of finding better thermoelectric materials among synthetic analogs of copper–chalcogenide minerals, we have synthesized iron-bearing colusites of a general formula Cu26−xFexV2Sn6S32. They crystallize in the cubic space group P-43n with the unit cell parameter increasing linearly with the iron content. At a low iron concentration, the crystal structure features disorder manifested by an anti-site effect and a shift of a part of the tin atoms from their ideal positions, which is absent for higher iron contents. The magnetization and 57Fe/119Sn Mössbauer studies showed that, for x = 1, iron is present as Fe3+, whereas for x > 1, Fe2+ and Fe3+ coexist. Additionally, weak antiferromagnetic interactions between iron atoms and fast on the 57Fe Mössbauer time scale (107–109 s−1) electron transfer between adjacent Fe2+ and Fe3+ centers were revealed. Thermoelectric studies showed that iron-bearing colusites are p-type semiconductors with low thermal conductivity stemming from their complex crystal structure and structural disorder. The highest ZT of 0.78 at 700 K was found for the x = 1 iron content, where iron is present as Fe3+ only.

Structure and Optical Properties of LixAg1–xGaSe2 and LixAg1–xInSe2

Complete substitution of Li atoms for Ag atoms in AgGaSe2 and AgInSe2 was achieved, resulting in the solid solutions LixAg1-xGaSe2 and LixAg1-xInSe2. The detailed crystal structures were determined by single-crystal X-ray diffraction and solid-state 7Li nuclear magnetic resonance spectroscopy, which confirm that Li atoms occupy unique sites and disorder only with Ag atoms. The tetragonal CuFeS2-type structure (space group I4̅2d) was retained within the entirety of the Ga-containing solid solution LixAg1-xGaSe2, which is noteworthy because the end-member LiGaSe2 normally adopts the orthorhombic β-NaFeO2-type structure (space group Pna21). These structures are closely related, being superstructures of the cubic sphalerite and hexagonal wurtzite prototypes adopted by diamond-like semiconductors. For the In-containing solid solution LixAg1-xInSe2, the structure transforms from the tetragonal to orthorhombic forms as the Li content increases past x = 0.50. The optical band gaps increase gradually with higher Li content, from 1.8 to 3.4 eV in LixAg1-xGaSe2 and from 1.2 to 2.5 eV in LixAg1-xInSe2, enabling control to desired values, while the second harmonic generation responses become stronger or are similar to those of benchmark infrared nonlinear optical materials such as AgGaS2. All members of these solid solutions remain congruently melting at accessible temperatures between 800 and 900 °C. Electronic structure calculations support the linear trends seen in the optical band gaps and confirm the mostly ionic character present in Li-Se bonds, in contrast to the more covalent character in Ga-Se or In-Se bonds.

Structure of racemic duloxetine hydro-chloride.

Duloxetine hydro-chloride (trade name Cymbalta) is marketed as a single enanti-omer (S)-N-methyl-3-(naphthalen-1-yl-oxy)-3-(thio-phen-2-yl)propyl-am-in-ium chloride, C18H20NOS+·Cl-, which is twice as effective as the (R)-enanti-omer in serotonin uptake. Here, we report the crystal structure of duloxetine hydro-chloride in its racemic form (space group Pna21), where it shows significant differences in the mol-ecular conformation and packing in its extended structure compared to the previously reported (S)-enanti-omer crystal structure. Mol-ecules of this type, comprising aromatic groups with a single side chain terminated in a protonated secondary amine, are commonly found in active anti-depressants. A Cambridge Structural Database survey of mol-ecules with these features reveals a strong correlation between side-chain conformation and the crystal packing: an extended side chain leads to mol-ecules packed into separated layers of hydro-phobic and ionic hydro-philic phases. By comparison, mol-ecules with bent side chains, such as racemic duloxetine hydro-chloride, lead to crystal-packing motifs where an ionic hydro-philic phase is encapsulated within a hydro-phobic shell.

Preparation and characterization of N-benzyl-2-methyl-4-nitroaniline (BNA) single crystals by physical vapour transport (PVT) technique

Good quality of N-benzyl-2-methyl-4-nitroaniline (BNA) single crystals (space group Pna21, point group mm2) having different morphologies were successfully grown from vapour phase for the first time by physical vapour transport technique under predefined supersaturation conditions. BNA single crystals of different morphologies resulted at different supersaturation conditions: prismatic (σ = 0.0218 to 0.1553), columnar (σ = 0.1553 to 0.4652), needle (σ = 0.4652 to 0.7245), fine-needle (σ = 0.7245 to 0.9166) and dendritic (σ = 0.9166 to 0.9729). The predicted theoretical morphologies using BFDH, and attachment energy models are in line with the experimental morphologies. The slice thickness, slice energy, attachment energy and anisotropic growth factor of different faces were determined which reveals that {020} are the slow-growing and morphologically important facets amongst others present in the grown BNA single crystal. Fast growth along ‘+c’ direction and no growth along ‘-c’ direction was identified due to the supersaturation-dependant anisotropic growth nature of BNA. Crystal purity and quality are confirmed by single crystal X-ray diffraction study. In addition, the role of intermolecular interactions, electrostatic, polarization, repulsion and dispersion energy components involved in the crystal packing to stabilize the BNA single crystal were characterized by the Crystal Explorer 17.5 software. Computed energy frameworks confirm that the dispersion energy component is predominantly contributing to the crystal packing than the Coulombic interaction energies.

Investigation of the Crystal Structure of Nd<sub>5</sub>Mo<sub>3</sub>O<sub>16 + δ</sub> in the Pressure Range 0–5.9 GPа

Neodymium molybdate with a cubic fluorite-like structure was obtained by solid state reactions from metal oxides. The formation of the final product occurs through the formation of a monoclinic structure of Ln2MoO6 type (space group C2/c) at 700°C, which probably contains vacancies in neodymium and oxygen lattices. Neodymium molybdate obtained at 900°C crystallizes in the space group Pn\(\bar {3}\)n with the cell parameter a ≈ 11.039 Å. The crystal structure of neodymium molybdate obtained at 700 and 900°C was studied by neutron diffraction and atomistic modeling using the GULP program in the pressure range 0–5.9 GPa, which demonstrated the stability of the cubic structure at elevated pressure.

Structural studies of a novel tautomeric Schiff base derived from 4-(N,N’-diethylamino)salicylaldehyde and 2-amino-4-methyl phenol: An experimental and theoretical study

A novel Schiff base, LMAP synthesized from 4-(N,N’-diethylamino)salicylaldehyde and 2-amino-4-methyl phenol has been characterized by single crystal X-ray diffraction and spectroscopic methods. DFT methods is used to investigate the enol-imine (EI) ⇄ keto-amine (KA) tautomeric behavior with respect to phase and in solvent media. The synthesized Schiff base crystallizes in the keto-amine (KA) form in the orthorhombic lattice and Pna21space group with four atoms per unit cell (Z = 4). Bond length analysis indicates that the KA form possesses significant zwitter ionic character. Study of electronic absorption and emission properties was conducted in the solid state as well as in different solvents. The UV–Vis result reveals the varied structural preference of the compound depending on the solvent media: polar protic solvents stabilize the KA form, while nonpolar and polar aprotic solvents favor the EI form. Quantum mechanical computations using DFT and TD-DFT also confirm these findings. Fluorescence emission spectra show multiple emission bands which indicate both excited state intramolecular proton transfer (ESIPT) and charge transfer (CT) phenomena occur simultaneously within the molecule. DFT predicted NLO responses of KA and EI were compared and found that the NLO response of KA is superior to that of EI.

Synthesis and Structure of RUB-58: An Almost Ordered, Highly Crystalline Member of the ZSM-48 Family of Zeolites

ZSM-48 describes a family of disordered high-silica zeolites with a one-dimensional pore system of straight 10-ring channels. Although many different synthesis procedures and various organic structure-directing agents have been tried, all ZSM-48-type materials produced to date have proven to be highly disordered. A few structural models were proposed by Schlenker et al. ( Zeolites 1985, 5, 355−358) and by Lobo and van Koningsveld ( J. Am. Chem. Soc. 2002, 124, 13222−12230) to describe the framework topology and the disorder of the real structure, but it has not been possible to refine the structure of a ZSM-48-type material using experimental diffraction data. RUB-58 was synthesized under hydrothermal conditions at 160 to 200 °C in the system SiO2/H2O/ethylenediamine/pyridine. The product consists of spherelike aggregates of small, needlelike, colorless crystals and has an X-ray powder diffraction (XPD) pattern similar to those published for ZSM-48-type materials. The pattern, however, contains a much larger number of sharp reflections indicative of a more ordered, crystalline material. The reflections could be indexed with the unit cell parameters a = 14.2095(3) Å, b = 20.0874(5) Å, c = 8.3752(2) Å in the space group Pna21, a sub-subgroup of Imma, which is the highest possible symmetry of the ordered ZSM-48 polymorph A (see the Database of Disordered Zeolite Structures). The structure analysis was performed in successive steps: (I) analysis of the average structure, which showed that the framework structure of RUB-58 can be described in terms of polymorph A and that the pyridine molecules occupy defined positions in the elliptical 10-ring channels; (II) refinement of a faulted structure using two separate, but identical polymorph A-type framework structures, with one shifted by exactly 0.5 of the unit cell along the channel direction (volume ratio: 92/8); (III) analysis of the structure of guest-free RUB-58 to examine the geometry of the channels in the empty framework (elliptical cross section nearly identical to that of the as-made material); and (IV) development of convincing disordered models to describe the real structure of RUB-58.

A novel Cu(II)-based DNA-intercalating agent: Structural and biological insights using biophysical and in silico techniques

A new mixed-ligand Cu(II) complex formulated as [Cu(dipic)(amp)(H2O)].H2O (dipic: pyridine-2,6-dicarboxylic acid, amp: 2-amino-4-methylpyridine), was synthesized and structurally characterized by FTIR spectroscopy, CHN analysis, and the single-crystal X-ray crystallographic method. The complex crystallizes in an orthorhombic space group Pna21, and the coordination environment around the metal center was found to be a pentacoordinate CuN2O2OW distorted square-pyramidal geometry. In order to systematically explore a detailed in vitro and in silico study of the DNA binding of the title complex, various biophysical (UV–Vis absorption spectroscopy, fluorescence, competitive binding with ethidium bromide) and theoretical (DFT, molecular docking simulation, and QM/MM) methods were applied which revealed that the complex could intercalate with the insertion of the amp ligand between the DNA base pairs. The experimental thermodynamic parameters of the interaction revealed the spontaneity of the process and the domination of the hydrophobic interactions in the association and stabilization of the DNA-Cu(II) complex adduct, which was in line with the docking and QM/MM data. In vitro cytotoxic potential of the complex against the human breast adenocarcinoma (MCF-7) cells was examined using MTT assay, which indicated that cancerous cells showed inhibition in presence of the complex.