CrystEngComm最新文献

In recent years, interest in 2D Janus materials has grown exponentially, particularly with regard to their applications in spintronics and optoelectronic devices. The defining feature of Janus materials is the ordered arrangement of different layer terminations - creating chemically distinct surfaces and an inherent out-of-plane polarity. Among the few known Janus materials, RhSeCl is particularly intriguing as a rare example of an intrinsic Janus compound. Owing to its exceptional chemical stability, RhSeCl offers a promising platform for exploring the physics related to the Janus-structure. However, synthesising large, high-quality crystals of this compound remains a significant challenge. Here, we report a novel synthetic pathway for growing crystals up to 6 mm in lateral size via a two-step self-selecting vapour growth reaction. We further present a comprehensive comparison of newly developed synthesis routes with all previously reported methods for RhSeCl. During these investigations, we identified a previously unreported impurity that forms in specific growth pathways and demonstrate how it can be avoided to obtain phase-pure few- and monolayer flakes. We showcase the reproducibility of the process to obtain high-quality, large single-crystals and flakes.

Digital holography and crystallography, regarded as separate fields, are converging to tackle a challenge in materials science: capturing the dynamics of crystal growth and transformation in real-time without disturbing the system. Here researchers spotlight free field-of-view infrared digital holography as a powerful, broadly applicable imaging strategy that bridges the gap in capabilities left by conventional X-ray, electron, and optical intensity-based methods. By simultaneously recording amplitude and phase with millisecond temporal resolution and deep penetration, infrared digital holography reveals hidden mesoscale processes, including asynchronous morphological phase evolution and stress defect coupling, across a wide range of crystalline systems, from minerals and salts to perovskite films and two-dimensional semiconductors. This capability not only complements atomic-scale probes like X-ray ptychography and four-dimensional scanning transmission electron microscopy, but also enables continuous, quantitative, phase-resolved imaging under ambient conditions. Infrared digital holography extends beyond academic inquiry, enabling precise crystal engineering, rapid discovery of functional materials, and integration with AI-driven analytics, thereby opening new avenues in crystallography with transformative implications for science and industry.

Correction for ‘Establishing σ-hole tetrel bonds by hemidirected lead(II) phosphonodithioates’ by Pretam Kumar et al., CrystEngComm, 2025, 27, 6386–6396, https://doi.org/10.1039/D5CE00611B.

New monotopic, ditopic, and tetratopic diethylamidinium building blocks were prepared and their interactions with (poly)carboxylates studied in solution and by crystallisation to give hydrogen-bonded networks. Crystallisation of the bis(diethylamidinium) tecton with terephthalate or biphenyldicarboxylate gave 1D hydrogen-bonded chains where the diethylamidinium groups adopted E/E conformations allowing for R²₂(8) hydrogen bonding with the anion. In contrast, 3D networks had E/Z diethylamidinium conformations, limiting hydrogen bonding to single-point interactions. Despite this, an open network structure was formed where approximately half of the unit cell volume was occupied by disordered solvent molecules. A survey of the Cambridge Structural Database revealed that both E/E and E/Z arrangements are common, while DFT calculations suggest that the E/E conformation is ∼13 kJ mol⁻¹ higher in energy than the E/Z conformation for both dimethylamidiniums and diethylamidiniums in the gas phase. Factors that contribute to the favourability of E/E and E/Z arrangements in the solid state are discussed, specifically with reference to the design of open networks.

Considerable ongoing research is aimed at enhancing the delivery of poorly soluble active pharmaceutical ingredients (APIs) via their complex formation with water-soluble cyclodextrin host compounds. The aim of the present study was to complex the potent steroidal hormones progesterone (PRO) and 17β-estradiol (BES) with heptakis(2,6-di-O-methyl)-β-cyclodextrin (DMB), and to characterize the resulting complexes for assessment of their potential utility. Complex synthesis using co-precipitation methods yielded single crystals of the desired complexes, which were subsequently characterized by thermal analysis, single-crystal X-ray analyses and solubility measurements. ¹H NMR spectroscopy indicated 1 : 1 host–guest stoichiometries for both of the hydrated complexes DMB·PRO and DMB·BES. Thermal analysis showed that the dehydrated DMB·PRO complex remained intact up to a temperature of ∼180 °C, when complex decomposition commenced. However, following the dehydration of DMB·BES, loss of the guest BES occurred in the approximate range 180–325 °C. Major findings were evident from X-ray analyses, which revealed only a single mode of API inclusion in the DMB·PRO crystal, but instead, the relatively rare phenomenon of bimodal API inclusion within the crystal of DMB·BES. Measurements of complex dissolution in a biorelevant medium at 27 °C showed significant API solubility enhancements of ∼25-fold for PRO and ∼40-fold for BES as a result of their inclusion in DMB.

Utilizing heterojunctions to their full potential represents a critical approach to addressing environmental pollution, though enhancing photocatalytic performance through this strategy remains challenging. In this study, a MoS₂-modified CdS heterojunction was synthesized via a hydrothermal method and served as an efficient photocatalyst for the degradation of organic pollutants. The composite was systematically characterized, and its photocatalytic activity was evaluated using organic dye rhodamine B (RhB) and the pesticide nitenpyram (NTP) as model pollutants. The results demonstrated a significant enhancement in photocatalytic efficiency for the MoS₂/CdS composite compared to pure CdS. Among the tested materials, the composite labeled MC4 exhibited the highest performance, achieving degradation rates of 90% for RhB and 89% for NTP within 90 minutes, corresponding to rate constants 4.4 and 2.9 times greater than those of pure CdS, respectively. Moreover, MC4 maintained high stability and catalytic activity over five cycling experiments. This work presents a low-cost and environmentally friendly route for synthesizing MoS₂/CdS composites, compliant with global demand for green and sustainable environmental solutions.

The combustion efficacy of propellants is crucial to the overall performance of rockets and missiles. Conventional propellant combustion catalysts suffer from toxicity and severe environmental pollution. To meet the demand for new green and non-toxic combustion catalysts, we synthesized three novel bismuth-based combustion catalysts, namely, [Bi₂(DHBQDC)(OX)₂(DMF)₆] 1, [Bi(BPSA)(PHON)(Ph)]·3DMF 2, and [BiO(TFPHA)H₂O]·H₂O 3, in this study. The structures of the catalysts were determined by single-crystal X-ray diffraction (SCXRD), and their thermal stability was investigated. Results demonstrated that all three catalysts exhibited excellent thermal stability, with the decomposition temperature of their organic frameworks exceeding 200 °C. In addition, differential scanning calorimetry and thermogravimetry were employed to study the thermal decomposition performance of the catalyst–RDX mixed systems. The introduction of these catalysts promoted the decomposition of RDX, leading to a reduction in the decomposition temperature of the systems to varying degrees and a decrease in the activation energy of the reaction. A high-speed camera was used to study the flame combustion performance of the mixed catalyst systems with RDX + NC/NG, which further confirmed the catalytic performance of various catalysts.

This work presents the synthesis, structural elucidation via X-ray diffraction, and density functional theory (DFT) investigation of three novel ligands based on deferiprone: maltol-TAU (3), maltol-histidine (4), and maltol-histamine (5), derived from taurine, histidine, and histamine, respectively. Additionally, the copper(II) complex of the histamine derivative, [Cu(maltol-HISTA)₂(H₂O)₂]·2H₂O·2HCl (6), was synthesized and characterized. In the solid state, the supramolecular architectures of ligands 3–5 and complex 6 are primarily stabilized by hydrogen bonding and $pi$-stacking interactions. Theoretical modeling corroborated these observations, confirming that compounds 3, 4, and 5 possess protonated imidazole rings accompanied by sulfonate, carboxylate, and chloride counter-ions, respectively. A distinct conformational variation was observed regarding ring orientation: the hydroxypyridinone and imidazole rings are positioned nearly orthogonally in 4, whereas they adopt a parallel arrangement in 5. DFT calculations were further employed to analyze specific supramolecular assemblies, with a focus on the structural influence of co-crystallized water molecules. To rigorously characterize the H-bonding and non-covalent interactions, quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) plot analyses were utilized, providing detailed insight into the electronic and structural features of these potential coordination chemistry candidates.

A unique lead perrhenate crown ether complex, [Pb(12-crown-4)(H₂O)(ReO₄)₂], exhibits an incommensurately modulated crystal structure at 101 K. In this (3 + 1)D superspace description, the ReO₄⁻ tetrahedra undergo continuous rotation. Describing their continuous rotation required introducing several constraints into the Legendre polynomials describing the displacive modulation of these atoms. At 296 K, the rotation of these tetrahedra is characterized by jumps between certain “stationary” positions. The average structure is monoclinic, P2₁/c with Z = 4, and can be described as comprising [Pb(C₈H₁₆O₄)(ReO₄)₂(H₂O)] ribbons. One half of the Pb²⁺ coordination sphere is occupied by the crown ether ligand, while the other is occupied by the oxygen atoms of water molecules and the perrhenate groups. The latter play two crystallographic roles: one bridging the PbO₈ polyhedra and the other acting as a terminal ligand with a very rare monodentate (κ¹) coordination. This is probably the reason for the nearly free rotation of these terminal ReO₄ groups along the Pb–O–Re axis. The structural chemistry of lead crown ether complexes, even those with relatively simple counteranions, is expected to yield a wide variety of unique and complex structures.

In recent years, rare earth ion doping has enhanced the luminescence performance of perovskite quantum dot (PQD) glass, but the enhancement mechanism caused by internal energy transfer deserves further study. In this work, a series of CsPbBr₃ PQDs doped with different concentrations of Tb³⁺ ions was prepared in a germanium borate glass matrix by the traditional melt quenching method and a heat treatment process. The experimental results indicate that after introducing Tb³⁺ ions into the PQD glass, the photoluminescence intensity was significantly enhanced by 11 times, and the photoluminescence quantum yield increased from 14.8% to 46.1%. The occurrence of this phenomenon can be attributed not only to the role of Tb³⁺ as a nucleating agent in PQD glass, which facilitates the formation of more small-sized CsPbBr₃, but also to its ability to replace Pb²⁺, thereby alleviating lattice distortion and passivating defects. Moreover, the core mechanism lies in the energy transfer process between Tb³⁺ and CsPbBr₃. It has been verified that there is not only a radiative photon reabsorption process in which Tb³⁺ releases photons that are absorbed by CsPbBr₃ but also a Förster resonance energy transfer process in which Tb³⁺ directly transfers energy to CsPbBr₃ in a non-radiative form. Finally, considering the differing thermal attenuation rates of Tb³⁺ and CsPbBr₃ in glass, a temperature-dependent luminescence color-tuning strategy is proposed, which has potential application value in the field of temperature sensing.