A novel coordination polymer (CP) was constructed applying Cu(II) as metal center and 2-aminoisonicotinic acid as organic linker, which exhibited thermal/solvent stability, N-2 adsorption resulting from structural porosity, and photothermal conversion efficiency g of 58.9%.

An Mn-based metal-organic framework (1@DMTA) was constructed by the solvothermal method. Subsequently, two more frameworks 1@MB and 1@RB were prepared through guest exchange by soaking 1@DMTA in methanol solutions of methylene blue chloride (MB center dot Cl) and Rhodamine B chloride (RB center dot Cl), respectively. The study revealed that the unidirectional helical distribution of coordinated carboxyl groups and metal ions led to helical chirality in 1@DMTA. The guest molecules of 1@DMTA were exchanged to construct the other two frameworks. Notably, after the exchange, the initial framework was preserved and chirality was inherited. An analysis of the single-crystal structures revealed Flack parameter values of 0.04 (2), 0.04(1), and 0.04(1) for 1@DMTA, 1@MB, and 1@RB, respectively, confirming their chirality, which agreed with the circular dichroism spectra. UV-Vis absorption spectroscopy, thermal stability analysis, photoluminescence spectroscopy, and theoretical calculations were also performed on the prepared materials.

The strong interfacial interaction between heterostructured semiconductors plays a vital role in enhancing the separation and transport efficiency of photogenerated charge carriers for photocatalytic applications. In this study, we report a stepwise synthesis strategy to fabricate a high-efficiency ternary heterojunction composed of NiS-decorated MoS2/CdS with strong interfacial bonding (NS@SI-MCS). Initially, an amorphous MoSx layer was deposited onto CdS nanorods via chemical bath deposition, followed by thermal treatment in a reductive H2/Ar atmosphere to form crystalline MoS2 with strong interfacial coupling. This treatment not only improved the crystallinity of MoS2 but also introduced sulfur vacancies, promoting enhanced interfacial contact and thereby strengthening electronic interactions and charge transport across the heterojunction. Subsequently, NiS nanoparticles were deposited as cocatalysts to facilitate efficient electron extraction and proton reduction. Comprehensive structural, optical, and electrochemical characterizations confirmed the formation of a well-integrated heterostructure, characterized by improved light absorption, suppressed charge recombination, and enhanced conductivity. The resulting NS@SI-MCS composite exhibited a remarkable hydrogen evolution rate of 5243 mu mol h-1g-1 under visible light, approximately 16.6 times higher than pristine CdS. This enhancement is attributed to the synergistic effects of strong interfacial coupling of MoS2/CdS and the catalytic contribution of NiS. This work provides valuable insight into designing strongly coupled heterojunctions and offers a scalable, noble-metal-free strategy for efficient solar-to-hydrogen conversion.

Molecular bridge isomerism plays a critical role in regulating electron transport and magnetic exchange within diradical systems of organic spintronics, yet polyfused thiophenic molecular bridges have not been thoroughly investigated. We report the design and synthesis of four novel diradical compounds employing nitronyl nitroxide (NN) radicals as spin sources and structurally defined tetra-thiophene (Tt) isomers as molecular bridges. The influence of the four isomeric Tt bridge with different alternative and spiral fused structure on magnetic coupling of Tt-NNs were systematically investigated through electron paramagnetic resonance (EPR), superconducting quantum interference device (SQUID) magnetometry, and density functional theory (DFT) calculations. DFT calculations reveal a direct correlation between spin interaction mechanism and magnetic coupling strength. Experimental results demonstrate that the isomeric arrangement of the tetra-thiophene bridge significantly modulates spin distribution in the ground state and electron delocalization capability. The Kekulé-type tetra-thiophene bridge (Tt-A), characterized by a continuous conjugation pathway, exhibits superior spin delocalization efficiency and strong antiferromagnetic (AFM) coupling (J/kB = -17.79 K, SQUID). In contrast, the nonKekulé-type isomers (Tt-B, Tt-C, and Tt-D) with disrupted conjugation show relatively weaker coupling, governed primarily by super-exchange interactions. Moreover, in bridge structures, a higher proportion of nonKekulé regions correlates with lower coupling strength.

Abstract C 13 H 12 O 2 S 2 , monoclinic, P 2 1 / n (no. 14), a = 8.9343(4) Å, b = 5.8480(3) Å, c = 24.3022(11) Å, β = 91.407(4) ∘ , V = 1269.35(10) Å 3 , Z = 4, R gt ( F ) = 0.0792, wR ref ( F 2 ) = 0.1833, T = 293 K.

Nitroaromatic explosives are hazardous substances, and their leakage poses severe threats to environmental safety, human health, and national security. Thus, the development of fluorescent probes capable of sensitive and rapid detection of nitroaromatic explosives is critically important. Although lanthanide-based metal-organic frameworks (Ln-MOFs) are widely investigated for this purpose, the development of ionic Ln-MOFs for nitroaromatic explosive detection remains significantly underdeveloped. Herein, we synthesized a novel cationic Eu(III)-MOF (NCULL) with a zwitterionic ligand, which is capable of rapid and highly sensitive detection of various nitroaromatic explosives in methanol, exhibiting an exceptionally low detection limit (LOD = 25.44 nM) for 2,4,6-trinitrophenol (TNP). To further expand the practical applications of NCULL, mixed-matrix membranes (MMMs) loaded with NCULL particles were fabricated. These MMMs not only achieved quantitative fluorescent detection of TNP in methanol solvent (LOD = 18.85 nM) but also could be regenerated by simple methanol washing. Furthermore, this study provides not only a prototype for the detection of various nitroaromatic compounds using cationic Ln-MOF but also offers a new example of efficient film-based detection in solutions.

Abstract C 12 H 36 AlN 3 O 15 S 6 , trigonal, R 3 ̅ $R̅{3}$ (no. 148), a = 11.2988(3) Å, c = 19.9379(7) Å, V = 2204.32(14) Å 3 , Z = 3, R gt ( F ) = 0.0397, w R ref ( F 2 ) = 0.0988, T = 100 K.

Abstract C 6 H 12 ClN 5 O 3 , monoclinic, P 2 1 / c (no. 14), a = 5.8165(4) Å, b = 19.6703(12) Å, c = 10.4258(5) Å, β = 116.380(3)°, V = 1068.63(11) Å, Z = 4, R gt ( F ) = 0.0372, w R ref ( F 2 ) = 0.0913, T = 100(1) K.

Achieving non-centrosymmetric (NCS) configurations in ABX3 -type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triplesite modulation strategy by synergistically tailoring the A -site cations (2-methylimidazole cation/1-ethyl3-methylimidazole cation), B -site metals (Sn2 + /Pb2 + ), and X -site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6 H11 N2 PbCl3 exhibits a moderately strong SHG efficiency of 3.8 x KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Organic ligand 4'-(4-(di-p-tolylmethyl)phenyl)-4,2':6'4''-terpyridine (gamma-dptpt) coordinated to metal salts (CoBr2 for 1, CdI2 for 2 and 3) to construct three coordination compounds. Single-crystal X-ray diffractions revealed that metal ions all have a 4-coordinate geometric structure. Compound 1 exhibits a zero-dimensional structure, while compounds 2 and 3 display one-dimensional band structures, attributed to coordination polymers (CPs). Thermogravimetry (TG) and photophysical properties also characterized.

Nitroaromatic compounds are widely utilized in medicine, dyes, spices, explosives, and other industries as raw materials. Among them, 2,4,6-trinitrophenol (TNP) is an extremely explosive and toxic compound. Hence, there is an urgent need for the development of new sensors to detect TNP. Herein, a novel binuclear Cd(II) metallocycle (Cd-HL) based on a tripod carboxylic acid ligand has been developed successfully. Interestingly, the unique crown-like Cd-HL can rapidly and selectively detect TNP in methanol with LODs of 0.91 mu M, which is more sensitive than many other TNP sensors. Furthermore, this stable Cd-HL is the first example of a Cd(II) metallocycle constructed by a tripod bridging ligand and brings new potential for the synthesis and design of lownuclearity supermolecular coordination complexes for detecting TNP in solution.

A chiral organic fragment was linked to tetraphenylethylene (TPE) to produce (4S)-5,5-dimethyl-2-[4-(1,2,2-trityl)phenyl]thiazolidine-4-carboxylic acid (TPCA). The absolute conformation of TPCA was confirmed by Flack parameter to definite the atomic positions. Based on the peripheral four benzene rings of the TPE, the in situ temperature-dependent crystal structure of TPCA was established to demonstrate the conformational change of TPCA in the temperature range from 165 to 298 K, further to investigate the physical mechanism of molecular motions for AIE phenomenon. The isotropic parameters of the individual benzene rings can further confirm the unequal vibrations of the molecule caused by the crystal anisotropy.

Establishing direct correlations between molecular motion, crystal structure, and macroscopic properties is essential for designing responsive functional materials. Herein, we report a malononitrile-based aggregation-induced emission luminogen (AIEgen), TPA-CN, that crystallizes into multiple polymorphs exhibiting distinct optoelectronic behaviors. In dilute solution, TPA-CN exhibits excitation-dependent emission spanning from sky blue to red under irradiation from 375 to 425 nm, arising from conformational flexibility and multiple excited-state transitions. In the solid state, subtle differences in crystal packing-governed by torsional angles and intermolecular interactions that modulate dipole moments-lead to pronounced variations in luminescence color and piezoelectric response. Mechanical grinding induces mechanochromic emission shifts without phase transitions, as confirmed by powder X-ray diffraction (PXRD). Comparative analysis of crystallographic data, Hirshfeld surface mapping, and non-covalent interaction (NCI) calculations reveals that weak intermolecular interactions critically regulate crystal packing, ultimately producing distinct emission colors and behaviors. Notably, the non-centrosymmetric polymorph (Pca21) exhibits strain-sensitive piezoelectric currents up to 562 pA under 0.51 % strain, with a piezoelectric coefficient (d33) of 1.77 pm & sdot;V-1 and a low Young's modulus of 6.75 GPa. Parallel device configurations further enhance mechanical sensitivity, enabling detection of micro-vibrations. This study reveals how minor conformational changes, and polymorphic packing can orchestrate dual photonic and piezoelectric functions, establishing a unified motion-structure-property paradigm. These insights advance the rational design of multifunctional organic materials for flexible sensing, soft electronics, and energy-harvesting applications.

π-magnetism of finite-sized nanoribbon occurring on the topological molecular interfaces remains largely unexplored due to limited experimental examples. Herein, we report rational design, solution synthesis and systematical characterization of a novel type of stair-like aza-nanographene (ANG) ANG-a~b with precise N-doping on the interfacial cove-edges. Within the same molecular π-backbone, ANG-a had a closed-shell structure due to the electronic perturbation of cove-edge substitution; while ANG-b hosted a spin-polarized interface state, and impressively its open-shell singlet diradicaloid structure produced a combined optoelectronic, magnetic and physicochemical characteristics. Besides, dicationic ANG-b was also synthesized and characterized as a ground-state diradicaloid, again closely associated with the interfacial spin-polarization in the charged π-system. Our studies might provide insights into future structural engineering of topological open-shell materials with robust yet exotic spin-polarized interface states.

The (thio)urea/base bifunctional activation catalyst system activates monomers or propagating alcohols through hydrogen bonding, demonstrating exceptional selectivity and activity. A series of economical cyclic (thio)urea-base combinations were employed as catalytic systems for rac-lactide and ε-caprolactone ring-opening polymerization (ROP). Among these, cyclic ureas combined with potassium methoxide (MeOK) exhibited superior catalytic activity over their thiourea counterparts, with the U3/MeOK system displaying remarkable controllability in rac-lactide polymerization, producing polymers with exceptionally low dispersity (Đ < 1.10). Kinetic studies confirmed that the polymerization process was well-controlled and adhered to first-order kinetics. Comparative analyses indicated that the dual hydrogen atoms on the urea moiety enhance the regulation of rac-lactide ROP. A plausible catalytic mechanism for the urea/MeOK system in rac-lactide polymerization was postulated. Additionally, in toluene solution, the urea/ MeOK system showed moderate catalytic performance for ε-caprolactone polymerization with reduced control, yielding poly(ε-caprolactone) of higher polydispersity. This study offers a straightforward approach toward the production of biodegradable polymeric materials.

Chemists are always seeking new methods to construct porous lattice frameworks using simple motifs as the impetus. Different from the extensively reported frameworks which were stabilized by extended bonding, porous crystals of discrete organic molecules is an emerging area of porous materials with dynamic and flexible conformation, consisting exclusively of non-covalent interactions. Herein we report geometrically simple linear molecule that assemble into a supramolecular nano-tunnel through synergy of anionic trident and multiple intermolecular pi-pi stacking interactions. The nano-tunnel crystal exhibit exceptional chemical stability in concentrated HCl and NaOH aqueous solutions, which is rarely been seen in supramolecular organic frameworks and often related to designed extensive hydrogen bonding interactions. Upon thermal treatment, the formed nano-tunnel crystals go through multistage single-crystal-to-single-crystal phase transformations accompanied by thermosalient effect. Aggregation-induced emission joins with the adaptive pores render the crystals with responsive fluorescent change from blue to yellow and visible self-healing porosity transformation upon being stimulated. Furthermore, the desolvated pores exhibit highly selective CO2 adsorption at ambient temperature.

Luminescent ligand 4-([4,2 ':6 ',4 ''-terpyridin]-4 '-yl)-N,N-diphenylaniline (tpatpy) was coordinated to MnX2 (X = Cl, Br) to construct two novel coordination polymers (CPs) by two-solvent interdiffusion, delivering compounds 1 (C66H48Br2MnN8) and 2 (C66H48Cl2MnN8). Single-crystal X-ray diffraction revealed that the two CPs both possessed microstructures of 2-dimensional layers which were tuned by six-coordinate Mn2+ ions. Compounds 1 and 2 display broad photoluminescent emission with intense peaks at ca. 468 nm, attributed to pi*-> n or pi*->pi transitions mixed with the ligand-to-ligand charge transfer (LLCT) transition. Their crystal structures, powder diffraction (PXRD) and thermogravimetry (TG) are also discussed.

Two novel chiral molecules, (4S)-5,5-dimethyl-2-(4-oxo-4H-chromen-3-yl)thiazolidine-4-carboxylic acid (OCCA) and (4S)-5,5-dimethyl-2-(4-(1,2,2-triphenylvinyl)phenyl)thiazolidine-4-carboxylic acid (TPCA), were successfully synthesized by aldehyde amine condensation reaction, and their structures were characterized by 1H NMR and single crystal X-ray diffraction. The intensities of photoluminescence changed with the aggregation, exhibiting that OCCA and TPCA are aggregation-induced emission luminogens (AIEgens). After complete aggregation, OCCA emitted the purple-blue light at the peak of 388 nm and TPCA emitted the cyan light at the peak of 488 nm. The aggregation-induced emission (AIE) effects for OCCA and TPCA resulted from local state to twisted intermolecular charge transfer (TICT) and restriction of intramolecular motion (RIM), respectively. Other spectra including UV-vis, IR, and Raman spectra were also discussed in detail.