A cross-shaped organic framework: a multi-functional template arranging chromophores.

This work explores the use of a cross-shaped organic framework that is used as a template for the investigation of multi-functionalized chromophores. We report the design and synthesis of a universal cross-shaped building block bearing two bromines and two iodines on its peripheral positions. The template can be synthesized on a gram scale in a five-step reaction comprising an oxidative homo-coupling macro-cyclization.

Elucidating the synergistic effect of oxygen vacancies and Z-scheme heterojunction in NU-1000/BiOCl-Ov composites towards enhanced photocatalytic degradation of tetracycline hydrochloride.

Although Z-scheme heterojunction composites have been widely studied in photocatalysis, in-depth investigation of oxygen vacancies (Ov) in the Z-scheme photocatalysts is still rare. Herein, an oxygen vacancies modified NU-1000/BiOCl-Ov composite with Z-scheme heterojunction was rationally designed and fabricated. The combination of X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) experiment verified the presence of oxygen vacancies, meanwhile the Z-scheme charge transfer across the heterojunction interface was confirmed in detail by the in situ-XPS, Kelvin probe force microscope (KPFM) studies, ultraviolet photoelectron spectroscopy (UPS), EPR radical capture experiment, as well as density functional theory (DFT) calculation.

Water-Pore Flow Permeation through Multivalent H-Bonding Pyridine-2,6-dicarboxamide-histamine/Histidine Water Channels.

Aquaporins (AQPs) are natural proteins that can selectively transport water across cell membranes. Heterogeneous H-bonding of water with the inner wall of the pores of AQPs is of maximal importance regarding the optimal stabilization of water clusters within channels, leading to selective pore flow water transport against ions. To gain deeper insight into the water permeation mechanisms, simpler artificial water channels (AWCs) have been developed.

Iron-Catalyzed SO-Retaining Smiles Rearrangement through Decarboxylation.

Radical Smiles rearrangements have emerged as powerful methodologies for constructing carbon-carbon bonds through intramolecular radical addition and fragmentation under milder conditions, with SO released as a byproduct. However, SO-retaining Smiles rearrangements, which can yield valuable alkyl sulfone derivatives, have been scarcely explored. In this study, we present an unprecedented iron-catalyzed SO-retaining Smiles rearrangement initiated by the decarboxylation of aliphatic carboxylic acids.

Rare-earth element doped NiFe-MOFs as efficient and robust bifunctional electrocatalysts for both alkaline freshwater and seawater splitting.

Based on the target of carbon neutrality, it is very important to explore highly active and durable electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a series of NiFe-based metal-organic frameworks (MOFs) with the doping of various rare-earth elements (Ce, Y, and La) were grown on nickel foam by a facile solvothermal process. The representative CeNiFe-MOF showed amazing OER performance with ultralow overpotentials of 224 and 277 mV at 500 mA cm in 1.

Regulating the Electronic Band Structure of the Ti-Based Metal-Organic Framework toward Boosting Light-Driven Hydrogen Evolution.

The photocatalytic H evolution rate on the isomorphic nanosheet-based Ti metal organic-frameworks (MOFs) is regulated through changing the length of aromatic carboxylate ligands. For the series of Ti-MOFs, when increasing the length of organic linkers, the band gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) narrow based on density functional theory (DFT) calculation, accompanied by a degree of increase of organic ligand involvement in the LUMO. When increasing the linker length, both the intensities of photoluminescence (PL) and electron paramagnetic resonance (EPR) signals related to Ti gradually decrease, which are opposite to their photocatalytic performance, where the longer the linkers, the higher the hydrogen evolution rate.

Mechanoelectric sensitivity reveals destructive quantum interference in single-molecule junctions.

Quantum interference plays an important role in charge transport through single-molecule junctions, even at room temperature. Of special interest is the measurement of the destructive quantum interference dip itself. Such measurements are especially demanding when performed in a continuous mode of operation.

Visualizing supramolecular assembly behavior, stimulus response, and solid state emission of higher-order Pt aggregates.

Here, we present the first instance of a highly efficient red tetramer aggregate with tunable emission based on a cationic platinum(II) complex in conjunction with a silver cluster anion counterpart. This system exhibits multicolor emission response behaviors, which can be conveniently and directly detected through spectroscopic analysis, showcasing intriguing luminescence changes. The self-assembly of Pt⋯, π-π, and hydrogen bonding interactions not only enables an intriguing color adjustment from green to yellow emission, and eventually to red emission, but also demonstrates the co-existence of the monomer, excimer, and aggregation.

Controlled synthesis of silver/silicon hybrid nanostructures enables enhanced photocatalytic CO reduction.

Localized surface plasmon resonances in plasmonic nanoparticles enable effective photon harvesting and generate energetic electrons and holes. However, fast charge recombination and surface contamination due to reactant-involved synthesis can significantly hinder the activity. Herein, we report a facile, solution-processed synthesis of hybrid uncoated silver nanoparticles combined with silicon nanocrystals to address these issues.

Long-persistent luminescence by host-guest Förster resonance energy transfer.

In this study, Förster resonance energy transfer (FRET) is harnessed to construct a novel stimulus-responsive long-persistent luminescence (LPL) system. Two organic molecules, DPSD and DPOD, were initially found to have no afterglow under ambient conditions, but exhibited prolonged afterglow upon friction with paper, showing a significantly promoted transition of triplet excited states. Substituting paper with α-cellulose (the main composition of paper) reveals a novel host-guest long afterglow system and allows for a deeper investigation of the above paper-promoted LPL phenomenon.

Promoting WLED-Excited High Temperature Long Afterglow by Orthogonally Anchoring Chromophores into 0D Metal-Organic Cages.

Afterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation-caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source.

A Cycloparaphenylene Acetylene as Potential Precursor for an Armchair Carbon Nanotube.

The bottom-up synthesis of carbon nanotubes (CNTs) is a long-standing goal in synthetic chemistry. Producing CNTs with defined lengths and diameters would render these materials and thus their fascinating properties accessible in a controlled way. Inspired by a recently reported synthesis of armchair graphene sheets that relied on a benzannulation and Scholl oxidation of a poly(p-phenylene ethynylene), the same strategy is applied on a cyclic substrate with a short, but well defined CNT as target structure.

Toward Molecular Textiles: Synthesis and Characterization of Molecular Patches.

This works describes a new step into the assembly of molecular textiles by the use of covalent templating. To establish a well-founded base and to tackle pre-mature obstacles, expected during the fabrication of the desired 2D-material, we opted to investigate the in-solution synthesis of molecular patches e. g.

Conjugated diamine cation based halide perovskitoid enables robust stability and high photodetector performance.

Low-dimensional lead halide materials have proved to be intrinsically stable semiconductor materials. However, the development of one-dimensional (1D) perovskites or perovskitoids with both robust water stability and high optoelectronic performance still faces significant challenges. Here, we report a new class of 1D (TzBIPY)PbX (X = Cl, Br, I) perovskitoids featuring a π-conjugated diamine cation (TzBIPY = 2,5-di(pyridin-4-yl)thiazolo[5,4-d]thiazole).

A Robust Adenine-Based Microporous Metal-Organic Framework with Hydrophobic Alkyl Groups and Abundant Lewis Basic Sites for CO/N Separation.

The development of a chemically robust metal-organic framework (MOF) with appropriate pore nanospace for efficient CO capture and separation from flue gas under humid conditions is sought after. Herein, an adenine-based microporous MOF, Cu-AD-SA, bearing abundant Lewis basic sites and alkyl groups has been utilized to capture and separate CO from CO/N gas mixtures. The introduction of alkyl groups enable Cu-AD-SA with high chemical stability.

Electronic Structure Regulation by Fe Doped Ni-Phosphides for Long-term Overall Water Splitting at Large Current Density.

Acquiring a highly efficient electrocatalyst capable of sustaining prolonged operation under high current density is of paramount importance for the process of electrocatalytic water splitting. Herein, Fe-doped phosphide (Fe-NiP) derived from the NiFc metal-organic framework (NiFc-MOF) (Fc: 1,1'-ferrocene dicarboxylate) shows high catalytic activity for overall water splitting (OWS). Fe-NiP||Fe-NiP exhibits a low voltage of 1.

NSPs: chromogenic linkers for fast, selective, and irreversible cysteine modification.

The addition of a sulfhydryl group to water-soluble -alkyl(-nitrostyryl)pyridinium ions (NSPs) followed by fast and irreversible cyclization and aromatization results in a stable S-C sp-bond. The reaction sequence, termed Click & Lock, engages accessible cysteine residues under the formation of -hydroxy indole pyridinium ions. The accompanying red shift of >70 nm to around 385 nm enables convenient monitoring of the labeling yield by UV-vis spectroscopy at extinction coefficients of ≥2 × 10 M cm.

Construction of Conjugated Organic Polymers for Efficient Photocatalytic Hydrogen Peroxide Generation with Adequate Utilization of Water Oxidation.

The visible-light-driven photocatalytic production of hydrogen peroxide (HO) is currently an emerging approach for transforming solar energy into chemical energy. In general, the photocatalytic process for producing HO includes two pathways: the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR). However, the utilization efficiency of ORR surpasses that of WOR, leading to a discrepancy with the low oxygen levels in natural water and thereby impeding their practical application.

Thermal control over phosphorescence or thermally activated delayed fluorescence in a metal-organic framework.

By integrating a tailor-made donor-acceptor (D-A) ligand in a metal-organic framework (MOF), a material with unprecedented features emerges. The ligand combines a pair of cyano groups as acceptors with four sulfanylphenyls as donors, which expose each a carboxylic acid as coordination sites. Upon treatment with zinc nitrate in a solvothermal synthesis, the MOF is obtained.

Triply Adaptive Libraries of Dynamic Covalent Macrocycles: Switching between Sorted and Unsorted States.

Dynamic noncovalent and covalent chemistries have enabled the constitutional modulation of chemical entities within chemical dynamic systems. The switching between order and disorder, i.e.