Journal of The Chinese Chemical Society最新文献

Designing luminophores with tunable emission properties is crucial for the development of responsive optical materials, such as pH-responsive compounds. Here, we report a structure–property investigation on a series of diphenyl-substituted aromatic structures S8 (2,6-diphenylnaphthalene), S11 (3,7-diphenylquinoline), and S14 (3,7-diphenylcinnoline) that vary by the number of nitrogen atoms incorporated into their aromatic cores. Through systematic photophysical characterization across multiple solvents, we demonstrate that nitrogen insertion progressively bathochromic-shifts absorption and emission bands while concurrently decreasing fluorescence quantum yield and excited-state lifetimes. To modulate this behavior, we employed both Brønsted acid protonation with trifluoroacetic acid (TFA) and Lewis acid coordination with tris(pentafluorophenyl)borane (BCF). Protonation induces red-shifted absorption and emission with solvent- and counter-ion-dependent fluorescence recovery, whereas BCF adduct formation in chloroform provides clean isosbestic behavior, quantitative suppression of non-radiative decay, and strong fluorescence turn-on. Time-resolved fluorescence studies and time-dependent density functional theory (TD-DFT) calculations support these findings, revealing that protonation effectively suppresses the n–π* and facilitates π–π* transitions. This study establishes a connection between nitrogen incorporation, protonation state, and emission behavior in 2,6-diphenylnaphthalene derivatives. The acid-triggered fluorescence activation observed in S14 highlights its potential as a promising platform for stimuli-responsive fluorescent probes, pH indicators, and molecular optical switches.

Supramolecular heterobimetallic lantern-shaped cages were self-assembled using ditopic ligands featuring both pyridine (py) and terpyridine (tpy) units anchored on a benzofuran backbone. These cages were constructed via coordination with Fe^II/Pd^II or Zn^II/Pd^II metal pairs, employing either a stepwise or one-pot synthetic approach. To enhance structural complexity, a second linear bisterpyridine ligand was introduced to elongate the lantern skeleton via spontaneous heteroleptic complexation. This strategy facilitated the formation of a supramolecular cage with dual metal centers and dual ligand types.

Photocatalytic degradation using nanoarchitecture materials remains a frontline technique for the remediation of aquatic pollutants, including food dyes, a crucial ingredient contributing positively to the food industry/production, while polluting the aquatic bodies. This paper aimed to review the remediation of food dye pollutants through photocatalytic degradation-oriented technology. Beyond evaluating the photocatalytic degradation performance of various nanomaterials, this study takes advantage of radical scavengers/electron trapping to elucidate the food dye photocatalytic degradation mechanism as part of the study's novelty. Another novelty of this work is in recyclability and real-life application studies, which are often neglected in many other reviews, and this was explored in this work to establish the industrial applicability/eco-economic benefits of nanomaterials. Notably, composite nanomaterials were found to be more efficient than the non-composites. Findings also revealed that, on average, various nanomaterials have an optimum photocatalytic degradation capacity of >75% for various food dyes and can be reused 2–10X while sustaining >70% of the original efficiency. The electron trapping analysis further showed that •OH and •O₂ are the leading radicals responsible for photocatalytic degradation activities. The use of artificial intelligence for better photocatalytic degradation mechanism interpretation/probing of radicals' participation is found to be an interesting area for future research.

Photocatalysis is an effective method for efficiently using solar energy and producing hydrogen through water splitting. In this study, we investigated an anchor group, chosen from carboxy, pyridyl, and tetrazole moieties, that easily attracts electrons from boron dipyrromethene (BODIPY) and injects them into titanium oxide (TiO₂) to synthesize a new dye-sensitized material for photocatalytic hydrogen production. Target BODIPY sensitizers were synthesized to yield 12%–29% with BODIPY-2-carbaldehyde and corresponding acetonitrile derivatives treated by piperidine or triethylamine as the catalyst. The coordination of the sensitizers onto TiO₂ was examined through attenuated total reflection Fourier transform infrared spectroscopy. The energy potential of BODIPY sensitizers with respect to TiO₂ was analyzed using cyclic voltammetry and differential voltammetry. The molecular orbitals of the BODIPY sensitizers were analyzed using density functional theory. Visible-light-driven photocatalysis with ascorbic acid as the sacrificial electron donor demonstrated hydrogen production. The photocurrent test showed that photo-induced electrons were injected into TiO₂ under visible light irradiation which supported dye-sensitized photocatalytic hydrogen production. The absorption spectra after the photocatalytic reaction showed no change in the pyridyl anchor group system, which suggested that the pyridyl-anchored dye-sensitized photocatalyst showed a good hydrogen production rate and stability.

Creating stable and well-defined porosity in supramolecular structures is a significant challenge due to the sensitivity of non-covalent interactions to environmental conditions. This study addresses this challenge by exploring the design and synthesis of extrinsic porous materials using giant tetrahedral molecules as fundamental building blocks within supramolecular frameworks. By incorporating multi-armed pyrene derivatives (Py_x) into a self-assembly system with a rigid giant tetrahedral molecule (tetraNDI), the charge-transfer (CT) interaction was utilized to guide the construction of robust supramolecular architectures. The geometric interplay between tetraNDI and the Py_x derivatives was found to be pivotal in determining the final structural forms, as the Py₄ and Py₃ interlock with tetraNDI to form a 1D columnar phase, whereas the Py₂ caps tetraNDI to form a 2D lamellar phase. Stable and precise molecular-level vacancies were identified in the porous supramolecular columns of tetraNDI:Py₃ by in situ temperature-dependent wide-angle X-ray scattering (WAXS) and thermal analysis. The findings not only extend our understanding of supramolecular chemistry but also offer a novel approach to the strategic design of porous materials, addressing the fundamental issue of environmental sensitivity in non-covalently bonded structures.

We report a base-mediated annulation of α-EWG-activated enone systems with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), affording dicyanobenzene derivatives via a sequential formal [4 + 2] cycloaddition and retrocyclization. In this process, DDQ acts as a dicyanoacetylene equivalent. The reaction is operationally simple and offers a modular route to electron-deficient aromatic scaffolds.

Metal oxide (MO_x)-based electrochemical sensors have emerged as highly effective tools for drug detection, offering several advantages such as high sensitivity, excellent stability, and versatile applications across various drug families. This review explores the use of different MO_xs, including iron oxide (Fe₃O₄, Fe₂O₃), manganese oxide (MnO₂, Mn₂O₃), titanium dioxide (TiO₂), copper oxide (CuO), zinc oxide (ZnO), cobalt oxide (Co₃O₄), nickel oxide (NiO), tungsten oxide (WO₃), and vanadium oxide (V₂O₅), in the electrochemical detection of drugs. The sensors based on these materials exhibit outstanding performance, with some achieving detection limits in the low nanomolar to picomolar range, making them ideal for detecting drugs at trace levels in biological fluids. Notably, iron oxide and manganese oxide sensors excel in detecting neurotransmitters, anticancer drugs, and antibiotics. In contrast, cobalt oxide and copper oxide are particularly effective for anti-inflammatory and analgesic drugs. Titanium dioxide and zinc oxide sensors demonstrate excellent stability and high sensitivity, making them suitable for clinical diagnostics and environmental monitoring. This review also discusses these sensors' linear range, detection limits, and practical applications in various therapeutic categories. Despite the promising results, challenges remain, such as enhancing sensor selectivity, reducing interference, and improving stability and reproducibility over time. Future advancements in nanocomposite materials and portable sensor technologies hold great potential for the widespread application of MO_x-based electrochemical sensors in real-time drug monitoring.

Achieving stable aqueous dispersions of graphene is crucial for enabling applications in flexible electronics, sensors, coatings, and biomedical materials. However, graphene's intrinsic hydrophobicity and strong tendency to aggregate in water remain major obstacles to its large-scale use. Non-covalent functionalization has emerged as a promising strategy to disperse graphene in water without compromising its sp²-conjugated structure. This minireview summarizes recent advances in non-covalent approaches employing small molecules, surfactants, and polymers to stabilize graphene dispersions. Key molecular interactions, such as ππ stacking, van der Waals forces, hydrophobic effects, and electrostatic or steric repulsion, are discussed. Particular emphasis is placed on pyrene derivatives, amphiphilic surfactants, and both synthetic and natural polymers, highlighting their dispersion mechanisms, performance, and limitations. The review concludes with perspectives on future developments, including the use of renewable, non-covalent modifiers to design efficient, scalable, and application-specific dispersion systems.

A series of A-DA'D-A type non-fullerene acceptors (NFAs) using benzimidazole (BIm) as the central acceptor (A') were developed. Side-chain engineering at the carbon-2 (C2) position (hydrogen or methyl or ethylhexyl) of the central imidazole moiety leads to the formation of three I-series NFAs, IM-H, IM-M, and IM-EH, respectively. The PM6:IM-M bulk heterojunction (BHJ) device demonstrated the highest power conversion efficiency (PCE) of 10.09% due to its better miscibility with the PM6 polymer. Furthermore, the planar-mixed heterojunction (PMHJ) devices of PM6/IM-M further improved the PCE to 12.68%. The observed enhancement can be attributed to the efficient charge transfer and the mitigation of recombination processes. Meanwhile, IM-M exhibited ambipolar charge transport behavior in organic field-effect transistor (OFET) devices, with balanced electron and hole mobilities of 0.028 and 0.024 cm² V⁻¹ s⁻¹, respectively.