Search Results (266)

The crystal structures of the 2-amino-5-halogenopyridines (halogen = Cl (1), Br (2)) and 2,3-diamino-5-halogenopyridines (halogen = Cl (3), Br (4)) were compared with respect to their intermolecular interactions. An ab-initio-based method for evaluating the interaction energies between molecules was employed to estimate the driving forces of crystal formation. As a result, regularities in crystal structure organization were identified. For compounds 1 and 2, a dimeric building unit is formed by two N–H…N_pyr hydrogen bonds. These dimers are further connected to neighboring units by C–H…π, C–H…N, N…X (X = Cl, Br), and non-specific interactions. The aforementioned intermolecular interactions give rise to layered structures that are similar but not isotypical. No significant contributions from π–π or N–H…N(H₂) interactions are observed in 1 and 2. The structures of 3 and 4 are isotypical and crystallize in the non-centrosymmetric space group P2₁2₁2₁. The most important intermolecular interactions are N–H…N_pyr, N–H…N(H₂), and stacking interactions. These interactions lead to identical columnar-layered structures in both 3 and 4. No significant contributions from halogen bonds of the type N…X (X = Cl, Br) are found in 3 and 4. Full article

The thioether-functionalized 2-azabutadienes (ArS)₂C=C(H)-N=CPh₂ (L1 Ar = Ph, L2 Ar = p-Tol) ligate to [Mn(CO)₅Br] to form the octahedral five-membered S, N-chelate complexes fac-[MnBr(CO)₃{(ArS)₂C=C(H)-N=CPh₂] (1 Ar = Ph; 2 Ar = p-Tol), whose crystal structures have been solved by X-ray diffraction. Complex 1 crystallizes in the non-centrosymmetric orthorhombic space group P2₁2₁2₁, whereas 2 crystallizes in the triclinic space group P$\overline{1}$. The secondary interactions occurring in the packing have also been assessed by an Atoms in Molecules (AIM) topological analysis. Full article

The controllable loading of a cocatalyst on a semiconductor is the key to further improving the efficiency and stability of visible-light photocatalytic hydrogen production. It is of great practical significance to load a cocatalyst onto a semiconductor spatially separated to realize space charge separation for efficient photocatalytic hydrogen evolution. The inherent anisotropic morphology of one-dimensional nanorods can provide two spatially separated locations at the tip and side surfaces of the nanorods. In this review, we systematically summarize non-centrosymmetric and centrosymmetric cocatalyst-tipped one-dimensional (1D) photocatalysts, including their preparation method, catalytic hydrogen production performance, and catalytic mechanism. This review will bring new vitality to the design, preparation, and application of cocatalyst-tipped one-dimensional nanorods. Full article

We investigate magnetic instabilities toward multiple-Q states in centrosymmetric bilayer triangular-lattice systems. By focusing on the interplay between the layer-dependent Dzyaloshinskii–Moriya interaction and layer-independent bond-dependent anisotropic interaction, both of which originate from the relativistic spin-orbit coupling, we construct a low-temperature phase diagram based on an effective spin model that also includes frustrated isotropic exchange interactions. Employing simulated annealing, we reveal the stabilization of three distinct double-Q phases in the absence of an external magnetic field, each characterized by noncoplanar spin textures with spatially modulated local scalar spin chirality. Under applied magnetic fields, we identify field-induced phase transitions among single-Q, double-Q, and triple-Q states, some of which exhibit a finite net scalar spin chirality indicative of topologically nontrivial order. These findings highlight centrosymmetric systems with sublattice-dependent Dzyaloshinskii–Moriya interactions as promising platforms for realizing a variety of multiple-Q spin textures. Full article

We numerically investigate the effect of multi-spin interactions on the stability of skyrmion crystals and other multiple-Q magnetic states, with a particular emphasis on the momentum-resolved bicubic interaction. By performing simulated annealing for an effective spin model that incorporates bilinear, biquadratic, and bicubic interactions on a two-dimensional triangular lattice, we construct the corresponding low-temperature phase diagram. Our results reveal that a positive bicubic interaction stabilizes a skyrmion crystal with a skyrmion number of two, whereas a negative bicubic interaction favors a single-Q spiral state. Moreover, we demonstrate that the stability region of the field-induced skyrmion crystal with the skyrmion number of one is largely enlarged in the presence of a positive bicubic interaction. Full article

The one-dimensional (1D) Sb(III)-based organic–inorganic hybrid perovskite (AImd)₂¹_∞[SbI₅] (AImd = 1-allylimidazolium) crystallizes in the orthorhombic, centrosymmetric space group Pnma. The structure consists of corner-sharing [SbI₆] octahedra forming 1D chains separated by allylimidazolium cations. Void analysis through Mercury CSD software confirmed a densely packed lattice with a calculated void volume of 1.1%. Integrated quantum theory of atoms in molecules (QTAIM) and non-covalent interactions index (NCI) analyses showed that C–H···I interactions between the cations and the ¹_∞[SbI₅]²⁻ network predominantly stabilize the supramolecular assembly followed by N–H···I hydrogen bonds. The calculated growth morphology (GM) model fits very well to the experimental morphology. UV–Vis diffuse reflectance spectroscopy allowed us to determine the optical band gap to 3.15 eV. Density functional theory (DFT) calculations employing the B3LYP, CAM-B3LYP, and PBE0 functionals were benchmarked against experimental data. CAM-B3LYP best reproduced Sb–I bond lengths, while PBE0 more accurately captured the HOMO–LUMO gap and the associated electronic descriptors. These results support the assignment of an inorganic-to-organic [Sb–I] → π* charge-transfer excitation, and clarify how structural dimensionality and cation identity shape the material’s optoelectronic properties. Full article

In this study, 3-chlorothiophene-2-carboxylic acid (HL) was used as a main ligand to successfully synthesize four novel complexes: [Cu(L)₂(Py)₂(OH₂)₂] (1), [Co(L)₂(Py)₂(OH₂)₂] (2) (Py = pyridine), [{Ni(L)₂(OH₂)₄}₂{Ni(L)(OH₂)₅}]L•5H₂O (3), and [{Co(L)₂(OH₂)₄}₂{Co(L)(OH₂)₅}]L•5H₂O (4). All four compounds were identified by elemental analysis and ESI mass spectrometry, and subsequently characterized by IR spectroscopy, UV-visible diffuse reflectance spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography, and cyclic voltammetry. X-ray analyses revealed that complexes 1 and 2 exhibit a centrosymmetric pseudo-octahedral coordination geometry; the copper (II) and cobalt (II) metal ions, respectively, are located at the crystallographic center of inversion. The coordination sphere of the copper (II) complex is axially elongated in accordance with the Jahn–Teller effect. Intriguingly, for charge neutrality, compounds 3 and 4 crystallized as three independent mononuclear octahedrally coordinated metal centers, which are two $\left[\mathrm{M}{\mathrm{L}}_2{\left({\mathrm{O}\mathrm{H}}_2\right)}_4\right]$ complex molecules and one ${\left[\mathrm{M}\mathrm{L}{\left({\mathrm{O}\mathrm{H}}_2\right)}_5\right]}^{+}$ complex cation (M = ${\mathrm{N}\mathrm{i}}^{\mathrm{I}\mathrm{I}}$ and ${\mathrm{C}\mathrm{o}}^{\mathrm{I}\mathrm{I}}$, respectively), with the ligand anion ${\mathrm{L}}^{-}$ serving as the counter ion. The anticancer activities of these complexes were systematically assessed on human leukemia K562 cells, lung cancer A549 cells, liver cancer HepG2 cells, breast cancer MDA-MB-231 cells, and colon cancer SW480 cells. Among them, complex 4 shows significant inhibitory effects on leukemia K562 cells and colon cancer SW480 cells. Full article

FmocFF is a highly versatile gelator whose π–π-stacking fluorenyl group and hydrogen-bonded peptide backbone permit gelation in a wide spectrum of solvents, providing a rich scaffold for crystal engineering. This study explores the synergistic effects of FmocFF organogels and solvent selection on controlling the polymorphic outcomes of nilutamide, a nonsteroidal antiandrogen drug with complex polymorphism. By systematically varying process parameters such as solvent type and concentration, we demonstrate remarkable control over crystal nucleation and growth pathways. Most significantly, we report the first ambient-temperature isolation of pure nilutamide Form II through acetonitrile-based FmocFF organogel, highlighting the unique interplay between solvent properties and gel fiber networks. Thermal analysis reveals that the organogel not only selectively templates Form II but also affects its thermal pathway. We also present compelling evidence for a new polymorph exhibiting second-harmonic generation (SHG) activity. This would represent the first non-centrosymmetric nilutamide form discovered, suggesting the gel matrix induces symmetry breaking during crystallization. We also characterize a previously unreported nilutamide–chloroform solvate through multiple analytical techniques including PXRD, DSC, FTIR, SXRD, and SHG microscopy. Our findings demonstrate that solvent-specific molecular recognition within gel matrices enables access to entirely new regions of polymorphic space, establishing gel-mediated crystallization as a broadly applicable platform technology for pharmaceutical solid form discovery under mild conditions. Full article

Based on the B-site modification strategy, excellent energy storage properties were achieved in this work by substituting Nb with Ta of the same valence in niobate-based glass ceramics. Ta substitution was found to lead to the transformation of crystal structures, and the space point group evolved from the non-centrosymmetric P4bm to the centrosymmetric P4/mbm, resulting in a transition from relaxor ferroelectric to paraelectric glass ceramics. Furthermore, the addition of Ta led to a significant decrease in grain size and interfacial activation energy, as well as an increase in the optical band gap, resulting in a dramatic increase in BDS from 800 kV/cm to 1300 kV/cm. The KBSN-4.0mol%Ta₂O₅ glass ceramic exhibited optimal energy storage properties, including a discharge energy density of ~5.62 J/cm³ and a superfast discharge rate of ~9.7 ns, resulting in an ultrahigh discharge power density of about ~1296.9 MW/cm³ at 1300 kV/cm. Furthermore, this KBSN-Ta glass ceramic also displayed good thermal stability over a temperature range of 20–120 °C, with the W_d decreasing by 9.0% at 600 kV/cm. B-site modification engineering in glass ceramics has proved to be an important way to effectively optimize energy storage performance. Full article

The misuse of fentanyl poses significant social risks, and accurately and swiftly detecting fentanyl in field settings presents a considerable challenge. Herein, we have designed and synthesized a fluorescent probe TP-CF₃-COOH, which is composed of carboxyl- and trifluoromethyl-binding center tetraphenyl butadiene. The unique centrosymmetric configuration of the TP-CF₃-COOH probe allows for the construction of a fluorescence “on–off” mechanism recognition platform by spatially matching fentanyl and its metabolite norfentanyl. Importantly, this study reveals that the interaction of fentanyl or norfentanyl with TP-CF₃-COOH results in spontaneous self-assembly, generating a three-dimensional complex sphere that is smaller than the two-dimensional sheet fluorescence probe. This self-assembly process results in the quenching of fluorescence. Theoretical calculations demonstrate that this process is accompanied by intermolecular through-space charge transfer during self-assembly, leading to a blue shift in emission wavelength. As a result, the TP-CF₃-COOH fluorescent probe enables the quantitative detection of fentanyl/norfentanyl within a range of 1 × 10⁻²–1 × 10³ μg/L, with limits of detection of 2 × 10⁻⁴ μg/L and 3 × 10⁻⁴ μg/L, respectively. This cost-effective, rapid, and sensitive fluorescent probe holds great potential for the onsite screening and detection of fentanyl and its analogues. Full article

Basic principles of ferroelectric activity induced by the noncollinear alignment of spins are reviewed. There is a fundamental reason why the inversion symmetry can be broken by certain magnetic order. This situation occurs when the magnetic order simultaneously involves ferromagnetic ($\mathit{F}$) and antiferromagnetic ($\mathit{A}$) counterparts, transforming under the spatial inversion $\mathcal{I}$ and time reversal $\mathcal{T}$ as $\mathcal{I}\mathit{F}=\mathit{F}$ and $\mathcal{IT}\mathit{A}=\mathit{A}$, respectively. The incompatibility of these two conditions results in breaking the inversion symmetry, which manifests itself in the electric polarization $\overrightarrow{P}$. The noncollinear alignment of spins is one of examples of such coexistence of $\mathit{F}$ and $\mathit{A}$. This coexistence principle imposes a constraint on possible dependencies of $\overrightarrow{P}$ on the directions of spins, which can include only “antisymmetric coupling” in the bond, ${\overrightarrow{\mathcal{P}}}_{ij}·[{\mathit{e}}_i\times {\mathit{e}}_j]$, and “single-ion anisotropy”, ${\mathit{e}}_i·$ $\overrightarrow{\mathbb{\Pi }}$ ${\mathit{e}}_i$. Microscopically, ${\overrightarrow{\mathcal{P}}}_{ij}$ can be evaluated in the framework of superexchange theory. For the single Kramers doublet, this theory yields ${\overrightarrow{\mathcal{P}}}_{ij}\sim {\overrightarrow{\mathit{r}}}_{ij}^{\phantom{0}}$, where ${\overrightarrow{\mathit{r}}}_{ij}^{\phantom{0}}$ is the spin-dependent part of the position operator induced by the relativistic spin-orbit coupling. ${\overrightarrow{\mathit{r}}}_{ij}^{\phantom{0}}$ remains invariant under spatial inversion, providing the microscopic reason why noncollinear alignment of spins can induce $\overrightarrow{P}$ even in centrosymmetric crystals. The symmetry properties of ${\overrightarrow{\mathit{r}}}_{ij}^{\phantom{0}}$ can be rationalized from the viewpoint of symmetry of Kramers states. Particularly, the commonly used Katsura–Nagaosa–Balatsky (KNB) rule $\overrightarrow{P}\propto {\overrightarrow{ϵ}}_{ji}\times [{\mathit{e}}_i\times {\mathit{e}}_j]$ (${\overrightarrow{ϵ}}_{ji}$ being the direction of the bond $ij$) can be justified only for relatively high symmetry of the bonds. The single-ion anisotropy vanishes for the spin ${\displaystyle \frac{1}{2}}$ or if magnetic ions are located in inversion centers, thus severely restricting the applicability of this microscopic mechanism. The properties of multiferroic materials are reconsidered from the viewpoint of these principles. A particular attention is paid to complications caused by possible deviations from the KNB rule. Full article

Four similar dinuclear lanthanide complexes have been synthesized by linking two [Ln(hfac)_2–3] units (hfac stands for hexafluoroacetylacetone) with different μ-O bridging ligands. The 2,2′-bipyridine-N-oxide ligand (bmpo) constructed two centrosymmetric complexes [Ln₂(hfac)₆(bmpo)₂] (Ln = Dy(1), Tb(2)), with nine-coordinated Ln^III ions showing C_s low symmetry, while the ligand di(2-pyridyl)methanediol (py₂C(OH)₂) formed another two compounds [Ln₂(hfac)₄(py₂C(OH)O)₂] (Ln = Dy(3), Tb(4)), with two kinds of eight-coordinated Ln^III ions exhibiting improved symmetries of D_4d and D_2d. Magnetic analysis reveals that Dy₂ complex 1 shows intramolecular antiferromagnetic coupling (J = −1.07 cm⁻¹) and no relaxation process above 2.0 K even in a 1000 Oe dc field, owing to the low symmetry of Dy^III ions, while the similar Dy₂ complex 3 with improved Dy^III symmetry shows ferromagnetic coupling (J = 1.17 cm⁻¹), which induces a 1000 Oe dc field-induced two-step magnetization relaxation processes with effective energy barrier U_eff = 47.4 K and 25.2 K for the slow relaxation and fast relaxation processes, respectively. This study proves again that the improved symmetry combined with intramolecular ferromagnetic interactions, both mediated by bridging ligands, can enhance the Dy^III anisotropy, further quench the quantum tunneling of the magnetization, and finally, enhance the magnetic behavior of Ln^III-based systems. Full article

We conduct a numerical investigation into the stability of a quadruple-Q skyrmion crystal, a structure generated by the superposition of four spin density waves traveling in distinct directions within three-dimensional space, hosted on a centrosymmetric body-centered tetragonal lattice. Using simulated annealing applied to an effective spin model that includes momentum-resolved bilinear and biquadratic interactions, we construct a magnetic phase diagram spanning a broad range of model parameters. Our study finds that a quadruple-Q skyrmion crystal does not emerge within the phase diagram when varying the biquadratic interaction and external magnetic field. Instead, three distinct quadruple-Q states with topologically trivial spin textures are stabilized. However, we demonstrate that the quadruple-Q skyrmion crystal can become the ground state when an additional high-harmonic wave–vector interaction is considered. Depending on the magnitude of this interaction, we obtain two types of quadruple-Q skyrmion crystals exhibiting the skyrmion numbers of one and two. These findings highlight the emergence of diverse three-dimensional multiple-Q spin states in centrosymmetric body-centered tetragonal magnets. Full article

In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea₂poh ligand have been isolated, and their molecular and crystal structures determined by single crystal X-ray diffraction. Potentiometric titrations were performed on a range of aqueous solutions in both systems, which allowed the identification of various complex species and afforded their stability constants. ESR spectra of samples with optimised concentrations of complexes in Cu(II)–L–H system were recorded. A distinguishing feature of both systems is the dimerization of anionic pseudo-macrocyclic complexes. The latter is caused either by centrosymmetric hydrogen bonding of the hydroxy group on the propane spacer to the oximato oxygen of the opposing unit or by back-to-back π-stacking of planar complex units. ESR measurements indicated likely coupling of Cu-Cu paramagnetic centres in the dimers. Full article

Inspired by the reported crystal structure of compound 1, we aimed to synthesize and determine the structure of compound 2, where two imidazolium (H₂im⁺) ions serve as diamagnetic countercations. Here, we report the thermal stabilities, FT–IR, visible, and RSE spectra, as well as the magnetic properties of both compounds. In these structures, µ-EDTA acts as a pentadentate chelator for both terminal Cu centers within the centrosymmetric linear trinuclear anion. The Cu(µ-EDTA) chelates bind to the central Cu(Him)₄ unit in subtly different ways: in compound 1, µ-EDTA has a free acetate arm and binds the central Cu(II) center through a syn,anti-carboxylate group. In contrast, in compound 2, the non-chelating acetate arm serves as a monodentate O-donor to the central Cu(II) atom, increasing the Cu(terminal)···Cu(central) distance from 6.08 Å in 1 to 6.80 Å in 2. Additionally, pairs of H₂im⁺ ions in compound 2 display antiparallel π-stacking interactions. We conclude that the H₂im⁺ counterions in compound 2 enable the magnetic isolation of the nearly identical trinuclear anion present in both compounds. DFT calculations further support the role of different interactions in stabilizing each crystal structure. In compound 2, dominant contributions from N–H···O hydrogen bonds and π-stacking interactions are accompanied by other, less conventional interactions, such as multiple C–H···O contacts and an O···CO(π-hole) interaction within the trinuclear anion. Full article