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The natural polymer cellulose exhibits significant potential for various applications due to its unique optical, electronic, and chemical properties. However, the use of cellulose materials in luminescent applications has been relatively limited. This study aims to develop a simple and efficient method to enhance the fluorescence of cellulose materials by incorporating rare earth elements, thereby expanding their range of applications. In this work, we synthesized hybrid cellulose materials by grafting Eu‐bpy (H2bpydc=2,2‐bipyridine‐5,5‐dicarboxylic acid) onto the surface of cellulose fibers through a straightforward post‐processing procedure, resulting in materials with excellent fluorescence properties. By leveraging the abundant hydroxyl groups on the surface of cellulose fibers, Eu‐bpy@CF exhibits high luminescence in response to relative humidity and pH changes, with a noticeable color shift from light red to red visible to the naked eye. Consequently, these materials were further applied in the construction of smart fluorescent switches for the highly accurate and selective detection of phenylenediamine. Our research provides a simple approach to creating environmentally responsive handheld fluorescent papers and expands the diversity of rare‐earth cellulose fibers for developing new fluorescent materials with smart functions. [ABSTRACT FROM AUTHOR]

In this work, barium sulfate (BS) fibers with a three‐level nanorod‐assembled hierarchical structure have been synthesized in a large scale by the barium oleate precursor hydrothermal method. A new kind of anti‐acid and anti‐alkali fire‐resistant BS inorganic paper has been developed using BS fibers, glass fibers and inorganic adhesive, and it has advantages such as high flexibility, good tensile strength, excellent fire‐resistant properties, excellent corrosion resistance to strong acids and strong alkalis. It is expected that the anti‐acid anti‐alkali fire‐resistant BS paper has promising applications under various high‐temperature and harsh conditions. [ABSTRACT FROM AUTHOR]

In this work, four POM‐based compounds containing viologen ligands were synthesized, namely {CuII(tybipy)2(DMF)2[H2(β‐Mo8O26)]2} ⋅ 4 C2H7N (1), (Htybipy)2 ⋅ (β‐Mo8O26) (2) (tybipy⋅Br=1‐Thiophen‐3‐ylmethyl‐[4,4']bipyridinyl‐1‐ium bromide), [CuII(nibipy)2(4,4'‐bipy)] ⋅ (SiW12O40) (3), (Hnibipy)2 ⋅ (δ‐Mo8O26) (4) (nibipy⋅Cl=1‐(4‐Nitro‐benzyl)‐[4,4']bipyridinyl‐1‐ium chloride, 4,4'‐bipy=4,4'‐bipyridine). In compounds 1 and 3, Cu2+ and mixed organic ligands modify POM anions. On the other hand, 2 and 4 are supramolecular structures only containing ligands and anions. Under Xe lamp with filter (300‐400 nm) irradiation, these four compounds showed good photoresponse and photochromic ability, which can be used in mixed matrix films for visible UV detectors. Compounds 1–4 also have photoluminescence property and show good fluorescence quenching effect. A suspension of four compounds can be evenly spread on filter paper as inkless and erasable printing materials. Compounds 1 and 2 were also used as Hg2+ fluorescence detectors. The fluorescence intensity of 1 decreased by ca. 90 % when the concentration of Hg2+ increased to 40 mM. Moreover, we also prepared composites 1/2@Hg2+,1@Cu2+, 1@Co2+ by introducing 1/2 and Hg2+, Cu2+ and Co2+ to detection paper respectively, which can act as photochromic materials with features of fast color recovery. [ABSTRACT FROM AUTHOR]

Paper spray ionization mass spectrometry (PSI‐MS) was used to detect a variety of species of hafnium and zirconium present in an aqueous acid solution containing NO3− and F− anions. This solution mimetics the acid waters used in separation/extraction processes. Hence, the information provided by PSI‐MS is combined with the results achieved from DFT calculations to confirm the nature and stability of each species. In the adopted experimental conditions, Zr(IV) appears coordinated with F−, NO3− and H2O to generate mainly the dimer [Zr2F3OH(NO3)2(H2O)5]2+, among other complexes, with remarkable thermodynamic stability (−48.7 kcal mol−1). On the other hand, Hf(IV) emerges predominantly coordinated with NO3− and F− anions. The hafnium monomers [HfF4NO3]− and [HfF3(NO3)2]− have thermodynamic stability related to the electron pairing of the valence layer. In the gas phase, the fluoroanions of Zr(IV) demonstrated a high electronic affinity and free energy via DFT (−156.7 kcal mol−1) correlating thermodynamic stability to the experimental (−47 kcal mol−1), for the formation reaction of [ZrF5]−. Besides, the presence of fluoride and nitrate in the reaction mixture induces the formation of dimers connected in μ2‐F bridges, with coordination 7 and 8 of the central atom. Finally, the results described herein are promising studies of chemical speciation of cationic metals in an aqueous environment, a challenging subject whose importance will grow in the coming years. [ABSTRACT FROM AUTHOR]

In this work, four POM‐based compounds containing viologen ligands were synthesized, namely {CuII(tybipy)2(DMF)2[H2(β‐Mo8O26)]2} ⋅ 4 C2H7N (1), (Htybipy)2 ⋅ (β‐Mo8O26) (2) (tybipy⋅Br=1‐Thiophen‐3‐ylmethyl‐[4,4']bipyridinyl‐1‐ium bromide), [CuII(nibipy)2(4,4'‐bipy)] ⋅ (SiW12O40) (3), (Hnibipy)2 ⋅ (δ‐Mo8O26) (4) (nibipy⋅Cl=1‐(4‐Nitro‐benzyl)‐[4,4']bipyridinyl‐1‐ium chloride, 4,4'‐bipy=4,4'‐bipyridine). In compounds 1 and 3, Cu2+ and mixed organic ligands modify POM anions. On the other hand, 2 and 4 are supramolecular structures only containing ligands and anions. Under Xe lamp with filter (300‐400 nm) irradiation, these four compounds showed good photoresponse and photochromic ability, which can be used in mixed matrix films for visible UV detectors. Compounds 1–4 also have photoluminescence property and show good fluorescence quenching effect. A suspension of four compounds can be evenly spread on filter paper as inkless and erasable printing materials. Compounds 1 and 2 were also used as Hg2+ fluorescence detectors. The fluorescence intensity of 1 decreased by ca. 90 % when the concentration of Hg2+ increased to 40 mM. Moreover, we also prepared composites 1/2@Hg2+,1@Cu2+, 1@Co2+ by introducing 1/2 and Hg2+, Cu2+ and Co2+ to detection paper respectively, which can act as photochromic materials with features of fast color recovery. [ABSTRACT FROM AUTHOR]

M-doped TiO2 and mixed oxides M xO y-TiO2 (M = V, Bi, W) were synthesized by the reactive mineralization of ash-free filter paper under anhydrous conditions. Mixtures of metal chlorides (TiCl4 with VOCl3, WCl6, or BiCl3) were reacted directly with cellulose, and three different Ti/M atomic ratios were used (99, 19, and 9). The resulting materials consist of original nanoflower assemblies of needle-shaped primary particles. Their physicochemical characteristics were investigated by various techniques (X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, electron microscopy, and elemental analysis). The incorporation of the doping metal or the formation of mixture of oxides with TiO2 (WO3, Bi2O3) depends on the metal and the proportions used. The photocatalytic activities of the materials were tested for the degradation of phenol. The vanadium-doped materials exhibit true solid-solution formation and their band gaps shift into the visible range. [ABSTRACT FROM AUTHOR]

Aristolochic acids (AAs) have caused widespread concern as highly nephrotoxic and carcinogenic substances. Therefore, it is essential to explore a simple and feasible method to detect AAs for disease prevention and clinical diagnosis. In this work, we designed and synthesized a novel luminescent metal organic framework (Zn-MOF), which has excellent structural stability and fluorescence stability. Notably, the luminescent Zn-MOF exhibits strong blue emission owing to ligand-centered electronic transitions, while being capable as a selective sensor for the quantitative detection of AAs in biological fluids with low detection limit. The fluorescence analysis method, possessing the advantages of reliability and high accuracy, further demonstrated that Zn-MOF has potential applications in monitoring the carcinogen biomarker AAs. Moreover, a paper-based sensor has been devised by depositing Zn-MOF on filter paper, which provides a novel strategy for visual, rapid, and on-site AAs detection with the naked eye. [ABSTRACT FROM AUTHOR]

This work contains synthesis of a di‐amide linker based Zr(IV) metal‐organic framework (MOF, 1) and its characterization with by PXRD, elemental analysis, FE‐SEM, EDX and FT‐IR analysis and application for the detection of toxic cyanide in aqueous medium. Furthermore, the physicochemical stability of the sensor was judged by the thermogravimetric analysis (TGA) and PXRD analysis. TGA curve of 1 displayed that the thermal stability of the probe was up to 230 °C. The MOF material was stable in sensing medium and in wide pH range (pH=2–8) which were confirmed by PXRD analysis of the recovered samples. The surface area (BET) of this porous sensor was 672 m2/g with a pore volume of 0.36 cm3/g at p/po=0.5. Guest free form of the MOF material (1') displayed its high efficiency for the fluorescence recognition of cyanide (CN−) with an extraordinary limit of detection of 76.4 nM in aqueous medium. Comparable recognition time (10 min) as the other available chemosensors of CN− ion and sensing of CN− using easily portable paper strips make this probe an extraordinary chemosensor for CN− ions. Together with paper strip based sensing, detection of CN− in apple seeds, various real water samples and wide ranges of pH solutions are the special features of the probe. The abstraction of amide proton by CN− ion favors "turn‐on" sensing, which was revealed by 1H‐NMR titration. This sensor of cyanide can also be used as luminescent switch due to its reversible nature of sensing. [ABSTRACT FROM AUTHOR]

The indirect detection of CO by using impregnated paper strips is reported. The ligand‐substitution reaction of cod by CO in an organometallic complex leads to the liberation of 1,5‐cyclooctadiene (cod), which can be smelled by the human olfactory system with very high sensitivity. Azolium salts tagged with methoxy polyethylene glycols (MeOPEG; 136, 750, and 2000 g/mol) were converted to the respective [IrCl(cod)(MeOPEG‐NHC)] complexes (NHC = N‐heterocyclic carbene). On reaction with CO, [IrCl(CO)2(MeOPEG‐NHC)] and 1,5‐cyclooctadiene are rapidly formed in virtually quantitative yield. Paper strips were coated with a thin film (1–10 µm) of an [IrCl(cod)(MeOPEG‐NHC)] complex. Exposure of the paper to low concentrations of CO (100 ppm) leads to rapid evolution of the strongly smelling olefin. [ABSTRACT FROM AUTHOR]

Copper‐based (Cu‐based) catalysts can efficiently convert carbon dioxide to multicarbon products by electrochemical reduction. In this paper, the electrocatalyst with the coexistence of three valence states of Cu(0)‐Cu(I)‐Cu(II) was successfully prepared by adjusting the experimental conditions. The catalyst was derived from Cu/Cu2O prepared on carbon cloth and exhibited excellent CO2 reduction performance. For carbon‐gaseous products, the Faradaic efficiencies for the Cu‐2 catalyst consisting of Cu(0)‐Cu(I)‐Cu(II) were 35.45±3.40 % at −1.66 V vs. RHE, of which 23.85±1.18 % for C2H4. And the synergistic effect of Cu(0)‐Cu(I)‐Cu(II) significantly improved the selectivity of the catalyst to C2H4. This paper provided an efficient method to rationally tune the valence state of Cu‐based catalysts to improve CO2 reduction performance. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) can effectively remove methylene blue (MB) from wastewater due to their abundant adsorption sites and multi‐level pores. In this paper, a copper‐based MOF: {[Cu ⋅ (L) ⋅ (H2O)] ⋅ (DMF)}n (1) (H2L=2‐hydroxyterephthalic acid; DMF=N,N‐dimethylformamide), was synthesized by hydrothermal synthesis method. X‐ray single crystal diffraction showed that a two‐dimensional structure was formed by the carboxyl group of L2− in 1 took μ2‐η1 : η1 bridged two adjacent Cu(II). In this two‐dimensional structure, the coordinated water molecules and hydroxyl group on L2− were distributed on the surface of 1. Thus, it had abundant adsorption sites. The transmission electron microscopy (TEM) of copper‐based MOF nano adsorbent showed that the particle diameter of the nano adsorbent prepared by a cell fragmentation apparatus was about 50 nm. The performance of the copper‐based MOF nano adsorbent in adsorbing MB indicated that the optimal adsorbent dosage was 0.20 g/L and the solution pH was 6. Under the optimal experimental conditions, its maximum adsorption capacity for MB was 143.3 mg/g, which was superior to most MOFs adsorbents. The adsorption thermodynamic analysis showed that the copper‐based MOF nano adsorbent at 25–45 °C was an exothermic (ΔH<0), and spontaneous (ΔG<0) process. [ABSTRACT FROM AUTHOR]

In this paper, a neutral copper iodide hybrid with unique Cu3I3 trimeric inorganic functional unit is successfully fabricated using 5,6,7,8‐tetrahydroquinoxaline (L) with large steric‐hindrance group as the organic ligand. The hybrid owns a one‐dimensional (1D) extended polymeric structure in the form of Cu3I3(L)2. As a CuI‐based hybrid, 1D‐Cu3I3(L)2 has an infrequent far‐red/near‐infrared emission, exhibiting the potential application prospects in the field of display and night vision. Moreover, the luminescence mechanism is carefully studied by decay lifetime measurement and calculation of density of states, which is verified to be the combination of metal‐to‐ligand charge transfer and halide‐to‐ligand charge transfer. [ABSTRACT FROM AUTHOR]

Inorganic‐organic hybrid solid electrolytes (HSEs) are an important category of electrolyte materials for solid‐state batterie. It is of interest and importance to investigate the influence of composition and content of inorganic fillers on the electrochemical performance of HSEs. In this paper, we fabricated HSEs using polyethylene oxide (PEO) as matrix and incorporating different inorganic powders as active fillers. A series of HSEs with different contents of Ga/Nb co‐substituted garnet oxide (Li6.35Ga0.15La3Zr1.8Nb0.2O12, GN‐LLZO) and Y‐doped Li29Zr9Nb3O40 (Li29.3Zr8.7Y0.3Nb3O40, 0.3Y‐LZNO) were carefully designed. The ionic conductivity of these PEO‐based HSEs were studied, and their performance in solid‐state lithium‐ion batteries with LiFePO4 (LFP) as cathode material and Li metal as anode were evaluated. The results showed that the HSE with addition content of inorganic powders, namely PEOLiTFSI@5 % GN‐LLZO +5 %0.3Y‐LZNO (noted as PL3) showed the optimized ionic conductivity of 2.9×10−4 S cm−1 at room temperature with an activation energy Ea of 0.21 eV. It has an electrochemical stability window of 4.65 V and ionic transfer number of 0.242. The addition of inorganic powders not only enhanced the ionic conductivities of PEO‐based HSEs, but also exhibited superior stability and interfacial compatibility with electrodes, leading to the improved cycle stability in the LFP/PL3/Li solid‐state battery configuration. [ABSTRACT FROM AUTHOR]

This paper tells the recent history of CO2 chemistry through the contributions from members of CIRCC to its birth and growth. Starting with the first transition metal complex bearing CO2 as a ligand synthesized in 1975 by the Aresta Group in Bari, the mode of bonding and the reactivity of coordinated CO2 are discussed. The early applications in chemo‐thermal, electrolytic, and biotechnological processes, and the use of SC‐CO2 as solvent and reagent are fields in which CIRCC partners have made pioneering contributions and continue to provide essential inputs. The paper is closed by highlighting key issues and challenges at stake, from capture to large‐scale conversion, investment infrastructure, progressive policies and standardized regulations needed to advocate carbon recycling as a pillar of future innovation in energy and chemical industries. CIRCC has been the nest of modern CO2 chemistry and the place where CO2 has always been considered a "resource" rather than a "waste". [ABSTRACT FROM AUTHOR]

We report heteroleptic ruthenium complexes of terpyridine (tpy) ligands with directly linked carboxylic acid anchors. These complexes feature methyl or methoxy‐substituted 4′−Phtpy as donor ligands. We prepared these heteroleptic complexes from the ruthenium (II) precursor via a milder route to preclude the homoleptic complex formation. The donor−acceptor arrangement of tpy ligands in these ruthenium complexes renders visible light absorption giving metal and ligand‐to‐ligand charge transfer excitations at c.a. 490 nm. We evaluate the effect of the tpy donor substituents on the light‐harvesting ability in Dye‐Sensitized Solar Cells (DSSCs) and compare their photosensitizing ability with heteroleptic complexes bearing phenyl spacer at the acceptor end. Further, scrutinizing their photovoltaic performance, we studied their electron transfer kinetics in DSSCs using electrochemical impedance spectroscopy. This paper presents the structure‐photosensitization relationship of these heteroleptic ruthenium complexes through a combined experimental and computational approach. [ABSTRACT FROM AUTHOR]

The epoxidation of propylene with dilute H2O2 aqueous solution over titanium silicalite‐1 (TS‐1) zeolite catalyst is a green chemical reaction for propylene oxide (PO) production. Carrying out the reaction in gas‐phase can get rid of problems caused by using methanol solvent. This paper reports an attempt of using non‐zeolite catalyst for the gas‐phase epoxidation. Amorphous Ti/SiO2, obtained by grafting amorphous SiO2 with TCl4 in ethanol solvent in a chemical liquid‐phase deposition (CLD) process, has been used as the catalyst. Results show that the CLD Ti/SiO2 with appropriate Si/Ti molar ratio is an active catalyst for gas‐phase epoxidation, achieving 9.8 % propylene conversion and 66.9 % PO selectivity with 40.3 % H2O2 utilization, which indicates that this amorphous Ti/SiO2 catalyst deserves extensive studies in the future. [ABSTRACT FROM AUTHOR]

Invited for the cover of this issue is the group of Hiroki Oshio at the University of Tsukuba, Japan. The cover image shows the metaphoric link between the synthesis of two new manganese clusters and the ancient Japanese art of origami. Origami literally means 'folded paper' and allows elaborate shapes to be created from the simplest materials, just like the rigid, planar ligands that were employed to 'fold' manganese ions into sophisticated helical superstructures. [ABSTRACT FROM AUTHOR]

Guest Editor Claudio Pettinari describes the organization of the first School of Organometallic Chemistry, telling the story of its development to become the highly successful International School anticipating its 13th edition in 2021. Bonati had always spent his time teaching to master and PhD students the most important topics in organometallic chemistry, and he was always convinced that transferring knowledge was the first activity a researcher had to perform. The new green deal is present in three papers, one describing dye-sensitized heterogenous photocatalysts for green redox reactions (Reginato), a second describing ion pair bifunctional catalysis in ionic liquids (Zanotti), and finally in a review on molecular sensitizers for photoelectrochemical water splitting (Abbotto). [Extracted from the article]

Grafting polymers from fluoropolymer backbones is very advantageous to modify the properties of these often non‐functional materials. It is particularly useful in the field of ultrafiltration membranes to tune the hydrophilicity of PVDF membranes and to add other properties such as antifouling for example. One of the main techniques used to effect such grafting is ATRP. A large number of papers are published every year on this topic. However, careful examination of this body of work reveals that the evidence provided to support the covalent bonding of polymer chains on the fluoropolymers are often limited and rather unconvincing. This is of course due to the difficult detection of the rare connecting covalent bonds. Nevertheless, this detection problem is not the only issue. Grafting from fluoropolymers using ATRP relies on the homolytic cleavage of C−F bond, notorious for their high stability and BDE. Moreover, fluoropolymers based on VDF are prone to dehydrofluorination by reaction with bases and nucleophiles, which leads to the formation of unsaturations within the polymer backbone. This reaction is often completely ignored even though ATRP ligands can trigger this elimination. These two very often overlooked reactivity features seriously question the use of ATRP as an efficient grafting technique for fluoropolymers. [ABSTRACT FROM AUTHOR]

In this paper we report the microwave assisted synthesis and characterization of a family of Na−Ln coordination polymers (CPs) of formula [NaDy2(MeCOO)2(SALOH)5(chpH)2] (1Ln, Ln=Eu, Gd, Tb, Dy, Ho, Y). The Na+ cations isolate Ln2 units in a one‐dimensional polymer. By changing the lanthanoid ions, we attain Single Molecule Magnet properties (1Dy), luminescent properties (1Eu, 1Tb, 1Ho), a diamagnetic material (1Y) and a material that presents magnetocaloric effect (1Gd). [ABSTRACT FROM AUTHOR]

Developments in the chemistry of weakly coordinating anions enabled isolation of numerous unique metal complexes with unusual ligands. An important example is the family of metal‐Fe(CO)5 complexes. In the current paper we present synthesis and thorough characterization of the first truly homoleptic {Cu[Fe(CO)5]2}+ cation obtained as a salt of weakly coordinating [Al(ORF)4]− (RF=C(CF3)3) anion. TGA/DSC/MS study show that its decomposition becomes noticeable only above 110 °C, thus it can be stored as powder in air‐free conditions for months. The crystal structure of {Cu[Fe(CO)5]2}+ shows strong asymmetry of the cation and very short Cu‐CO bonds in comparison to analogous {M[Fe(CO)5]2}+ where M=Ag or Au. Characterization is complemented with analysis of vibrational spectra and extensive DFT calculations which give insight into the energetics of Cu+‐Fe(CO)5 systems. Our results show that {Cu[Fe(CO)5]2}+ is homoleptic only as salt of [Al(ORF)4]−. Furthermore, in the presence of additional, even weakly basic ligands, the Cu+‐Fe(CO)5 bond strength decreases what may contribute to the complex's instability in liquid SO2 or in the presence of [SbF6]−. These conclusions point at the key role of selection of proper anion and solvent in stabilization of these types of complexes. [ABSTRACT FROM AUTHOR]

This paper describes the rare use of a 6‐membered saturated N‐heterocyclic carbene (NHC) known as 1,3‐di(2,6‐diisopropylphenyl) tetrahydropyrimidine‐2‐ylidene (abbreviated as 6‐SIDipp) as a ligand in zinc chemistry. We report on the investigation of the reactions between 6‐SIDipp and ZnX2, which resulted in a range of new monomeric 6‐SIDipp⋅ZnX2 complexes (X=Et (1), Cl (2), Br (3), and I (4)). We also prepared a new NHC zinc complex where the two substituents of the zinc atom are different, 6‐SIDipp⋅Zn(Et)Br (7) through the reaction of the proligand [6‐SIDippH]Br with ZnEt2. We have observed that the reactions of complex 1 with sulfur and HBpin led to the removal of the ZnEt2 moiety, resulting in the formation of a C=S double bond and a B−H activation product, respectively. Lastly, the reaction of 1 with five‐membered NHCs led to the exchange of carbene and the formation of either 5‐IDipp⋅ZnEt2 (8) or 5‐SIDipp⋅ZnEt2 (9). [ABSTRACT FROM AUTHOR]

This paper describes the synthesis of a new acetylene‐bridged triphosphine, ((phenylphosphanediyl)bis‐(ethyne‐2,1‐diyl))bis(diphenylphosphane) [PhP{C≡CPPh2}2] (2) and its coordination complexes of RuII, RhIII, CuI, PdII and PtII. The reaction of diethynylphenylphosphine [PhP{C≡CH}2] (1) with two equivalents of LiHMDS followed by the addition of PPh2Cl resulted in 2. Treatment of 2 with [Ru(η6‐p‐cymene)Cl2]2 and [RhCp*Cl2]2 in 1 : 1.5 molar ratios produced trinuclear complexes [{Ru(η6‐p‐cymene)Cl2}3{μ3‐PPh(C≡CPPh2)2}] (3) and [(RhCp*Cl2)3{μ3‐PPh(C≡CPPh2)2}] (4). The molecular structure of 3 was confirmed by single crystal X‐ray analysis. Treatment of 2 with M(COD)Cl2 (M=Pd, Pt) in 2 : 3 ratio afforded open book type complexes [(MCl2)3{μ3‐PPh(C≡CPPh2)}2] (5 M=Pd, 6 M=Pt). The reaction of 2 with CuI in 1 : 2 ratio afforded 1‐D coordination polymer [{Cu2(μ2‐I)2(CH3CN)}{PPh(C≡CPPh2)2}3{CuI}2] (7) containing [(CuI)2{μ2‐(P−C≡C−P)3}] cylindrical units. [ABSTRACT FROM AUTHOR]

Catalysis inside molecular cages and capsules has attracted an increasing amount of attention over the last decade. While many examples of the catalysis of reactions with cationic intermediates and transition states are known, those with anionic counterparts are scarce. One limiting factor is access to suitably sized cationic iminopyridine‐based cages that are stable towards water and anionic/nucleophilic guest molecules. This study aimed at identifying such suitable cages. In this full paper, we describe the journey that finally led to the synthesis of a novel iminopyridine‐based tetrahedron that can bind larger organic anions with binding constants of up to 850 M−1 in MeCN−d3/H2O=9 : 1. Importantly, it also displays stability in basic aqueous acetonitrile. Surprisingly, investigations towards catalysis of reactions with anionic transition states did not indicate rate accelerations in the presence of the cage. [ABSTRACT FROM AUTHOR]

In this paper, we present the high‐pressure/high‐temperature synthesis and characterization of the potassium fluoridooxidoniobate K3Nb2O4F5. Single‐crystal analysis revealed that the phase crystallizes in the trigonal space group R3‾ ${R\bar{3}}$ m (hR18) with a=5.799(2), c=21.371(4) Å, V=622.4(4) Å3 and Z=3 at T=299 K exhibiting a structure type closely related to that of Ba2RbFe2F9. The assignment of the anion positions to oxygen and fluorine is based on crystallographic data and BLBS/CHARDI calculations. Further characterization via EDX spectroscopy was carried out, corroborating the ratio of K to Nb. Doping of the title compound with Mn4+ was achieved in a secondary step using a ball‐mill, resulting in a red phosphor material, which was additionally analyzed by luminescence spectroscopy. The emission maximum is located at λmax=630 nm. [ABSTRACT FROM AUTHOR]

Layered transition metal oxides (layered materials) have the advantages of simple synthesis methods, high average operating voltages, and good specific capacity, and are therefore promising cathode materials for sodium‐ion batteries (SIBs). However, the capacity retention of these materials is poor due to the dissolution of transition metals caused by the detrimental reactions of the electrode with the electrolyte and the rupture of the electrode due to volume expansion during cycling. Studies have discovered that surface modification can effectively improve the aforementioned problems. This paper reviews the effects of different coating materials (e. g., carbon coatings, metal oxide coatings, phosphate coatings, etc.) on the performances of layered cathode materials and analyzes the reasons for the improved performance. In addition, the limitations of different coating materials and coating methods are presented, and future developments are proposed. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting to obtain hydrogen energy can transform low‐density solar to high density, new and clean energy in a clean way, which is one of the ideal ways to solve the energy crisis and environmental pollution. In this paper, The CoxP/hollow porous C3N4 composite photocatalytic material was synthesized by simple methods. The photocatalytic hydrogen production rate of CoxP/hollow porous C3N4 reaches 1602 μmol g−1 h−1, which is 151 times of that of pure C3N4. The reasons for the high photocatalytic H2 evolution activity of CoxP/hollow porous C3N4 could be summarized as follows: (1) the hollow and porous structure of C3N4 shows higher light capture efficiency, larger specific surface area and more surface active sites. (2) metalloid CoxP loaded forms the Schottky contact with C3N4, which improves the photogenerated charges separation efficiency of C3N4, prolongs the photogenerated charges lifetime and improves the photocatalytic H2 evolution activity of C3N4. (3) The higher conductivity of metalloid CoxP and the lower overpotential of hydrogen production are other reasons for the higher activity of photocatalytic hydrogen production of CoxP/hollow porous C3N4. This work provides an important role for the design of efficient, stable, and efficient construction of photocatalysts for solar energy conversion. [ABSTRACT FROM AUTHOR]

Polar vinyl polymers, a class of polymers with polar groups as side chains, have significant advantages over conventional nonpolar polyolefin materials in terms of viscosity, toughness, interfacial properties (dyeability and printability), and compatibility with solvents or other polymers. Among them, aromatic polar vinyl polymers are of interest because of their good heat resistance properties. In addition, stereoselective polymerization of aromatic polar vinyl monomers has been rapidly developed because the steric structure of the polymer has a significant impact on its physical properties. In this paper, we review the research progress of stereoselective polymerization catalysts for aromatic polar vinyl monomers in recent years, discuss in detail the influence of ligand structure, electronic effect of substituents, spatial site resistance effect, central rare earth metal species and polymerization solvents on the activity and stereoselectivity of polymerization reactions, and explore the possible mechanism of polymerization reaction. [ABSTRACT FROM AUTHOR]

Visible light‐driven photocatalysis has gained much attention due to its light‐harnessing characteristics and is extensively used in wastewater remediation. This paper presents a novel oxygen‐deficient manganese antimonate, MnSb2O6‐x, with a trirutile structure as an effective visible‐light‐driven photocatalyst for dye degradation. The synthesized samples were subjected to XRD, UV‐Vis DRS, SEM‐EDS, Raman, XPS, and PL analyses to study their physic chemical properties. The influence of sequential or single heating during the preparation method on the generation of oxygen vacancies is evaluated using UV‐Vis DRS, XPS, ESR, and Raman techniques. The oxygen‐deficient MnSb2O6 could achieve up to 85 % of MO degradation in 180 min under visible light irradiation, and its reusability up to six cycles was also investigated. In addition, the mechanism of dye degradation was supported with a scavenger test, and the degradation activities are correlated to the electron‐hole pair separation as convinced from the PL spectra. The simple and unique method of oxygen vacancy generation can inspire the development of antimonates with oxygen deficiencies, which have significant scope of application in environmental and energy conservation. [ABSTRACT FROM AUTHOR]

Electrochromic supercapacitors have received extensive attention owing to their ability to combine electrochromism and energy storage properties. In this paper, a bifunctional electrode material based on Preyssler‐type tungstophosphate (P5W30), polyelectrolyte poly(allylamine hydrochloride) chain (PAH) modified by the iron complex (Fe(phen)3) was synthesized by Layer‐by‐Layer method (LbL). Compared with the film without PAH, the composite film displays large optical contrast (35.17 %), fast response time (2.49/0.90 s for coloring/bleaching), great coloration efficiency (94.73 cm2 ⋅ C−1) and high specific capacitance (10.45 mF cm−2). Moreover, the good cycling stability (83.66 % retention of the original optical modulation after 1500 cycles, capacity retention rate is 91.46 % after 500 cycles) is achieved. In addition, the composite film is also able to visually detect the energy storage level through reversible and rapid color changes, and further use it to assemble device. This work provides an promising candidate for electrochromic and energy storage devices. [ABSTRACT FROM AUTHOR]

Metal catalyzed polymerizations are among the most important chemical reactions, accounting for the production of about 400 million tons per year of polymeric materials, 50 % of which are polyolefins. The CIRCC research units at the University of Salerno, founded by the late Professor Adolfo Zambelli, a coworker of Giulio Natta and a pioneer in the studies of stereospecific polymerization catalysts, has a consolidated expertise in this field. Although often considered a "mature" area of research, olefin polymerization catalysis continues to drive great interest of both industrial and academic scientists. On the other hand, strong political and economic pressure toward the development of "green" and possibly biodegradable alternatives to olefin‐based polymers stimulated our group to direct increasing research efforts in the area of sustainable polymers. In this perspective, we focus on the most recent work from the CIRCC research units involved in homogeneous catalysis for polymerization of a variety of monomers, with the aim to address how the concepts and the expertise developed for olefin polymerization can be applied to the development of different metal‐catalyzed polymerizations and copolymerizations. Of course, although the results are discussed in the frame of the most important literature contributions, a comprehensive review of such a wide and diversified topic is out of the scope of the paper. References to reviews covering the different types of metal catalyzed polymerizations are provided in each chapter. [ABSTRACT FROM AUTHOR]

In this paper, we report the Yb(OTf)3‐mediated etherification reaction that allowed obtaining R,R and S,R isomers of ferrocenyl glycol nucleic acid (Fc‐GNA) nucleosides from their corresponding stereo‐defined (S,R) precursor. The R,R absolute configuration of the chiral carbon atoms in one of the Fc‐nucleoside isomers was assigned by single‐crystal X‐ray diffraction. Density functional theory calculations showed that the stereochemical outcome of the reaction can be explained by an exo attack of ethylene glycol on the pro‐R‐ or pro‐S‐configured α‐ferrocenyl carbenium ion intermediate. The R,R isomer was transformed into the corresponding nucleotide diethyl ester which is, to the best of our knowledge, the first Fc‐GNA nucleotide ever reported. The obtained compounds feature reversible one‐electron oxidation of the ferrocenyl portion of their molecular structures. Anticancer activity studies showed that the (S,R) nucleoside was the most active against HeLa and Ishikawa cancer cells, while it did not show any activity against nontumorigenic L929 cells. The compound induced apoptosis in HeLa cells at IC50=66.0 μM concentration upon 72 h of treatment. [ABSTRACT FROM AUTHOR]

In this paper we study the post-synthetic modification (PSM) reaction on solid spin crossover (SCO) [Fe(NH2trz)3]X2 (X=NO3, OTs, Cl, SO4, BF4) complexes with different substrates. The wide access to a diversity of functionalized complexes with imine, amide and carbamide groups from the same amino parent compound demonstrates the synthetic approach value of this method. The as-obtained post-synthetic complexes were studied by IR, solid NMR, elemental analyses, and powder X-ray diffraction, and compared to the corresponding compounds obtained by direct synthesis (DS) routes. Moreover, after digestion of the complexes obtained by PSM reactions, the free ligands were characterized by NMR in solution, which allowed us to indirectly confirm the formation of complexes we wished to synthesize. The study reveals in numerous cases that a complete post-synthetic modification is possible despite the structural cohesion that is established between the 1D coordination chains within these materials. Spin crossover properties of some complexes obtained by both methods are also reported and compared. [ABSTRACT FROM AUTHOR]

The paper reports on the synthesis and evaluation of photochemical properties of gold nanorods (Au−NRs) coated with PEG with a thiol (−SH) group or SiO2 and their physical mixtures with pheophorbide a. Also biological activity of these systems was tested in photodynamic therapy directed towards Staphylococcus aureus. The potential additive effect between differently functionalized Au−NRs and the dye pheophorbide a was also studied. The efficiency of singlet oxygen generation varied considerably depending on the type of PEG polymer used for coating NRs and was the highest, of 65%, for the polymer PEG (10k) and the Au−NRs concentration of (1.33×10−11 M). For the other studied PEGs (2k, 5k) and the same concentration of NRs, a decrease in the singlet oxygen generation efficiency was observed. The most effective against Gram‐positive bacteria were the mixtures of PEG‐coated Au−NRs with pheophorbide a, exposed to irradiation at 405 nm and 660 nm, which provided a >5.8 log reduction in the bacteria growth. However, no strong bactericidal effect was noted in the case of irradiation with 525 nm. [ABSTRACT FROM AUTHOR]

Our search of new organopalladium compounds able to promote an effective antiproliferative action towards ovarian cancer cells continues. In this paper we have examined for the first time the anticancer activity of palladium imidoyl complexes, for which two different types of phosphines have been chosen as ancillary ligands: i) PTA and DAPTA to take advantage from their solubility in aqueous environment, and ii) dppf for combining the action of the Pd‐imidoyl fragment with that, well‐known, of ferrocene. The synthetic protocols as well as the exhaustive characterisation of the complexes through spectroscopic and diffractometric methods are described. In vitro tests carried out to assess the cytotoxicity of the new compounds towards two ovarian cancer cell lines (one cisplatin sensitive and the other cisplatin resistant) have revealed an interesting effect of the halide coordinated to the palladium centre (halogen effect). Moreover, all complexes have shown the same activity against the cisplatin‐sensitive (A2780) and cisplatin‐resistant (A2780cis) cell lines, suggesting a different mode of action with respect to the "classical" platinum‐based drugs. Finally, a selection of the most active compounds has shown an interesting selectivity towards ovarian cancer cells. [ABSTRACT FROM AUTHOR]

Finding efficient materials for treatment of dye wastewater is a hot research topic in the field of environmental science. In this paper, the mono‐lacunary polyoxometalate anion (SiW11) is completely sealed in a zeolitic imidazolate (ZIF‐8) polyhedron, forming a new polyhedral absorbent, SiW11@ZIF‐8, with an intact surface and a negative charge center. Unlike saturated Keggin type polyoxoanions, SiW11 is only stable under neutral conditions and does not release any protons in solutions. Therefore, SiW11@ZIF‐8 does not display the usually observed acid‐induced etching and shows effective and ultrafast adsorption for the cationic dye methylene blue. This work not only indicates that the neutral polyoxoanion is a more suitable candidate to be sealed in ZIF‐8 to form a stable unpunched composite, but also provides a new concept for the design of stable polyoxometalate@ZIF adsorbents to be potentially used in the treatment of cationic dyes in wastewater. [ABSTRACT FROM AUTHOR]

This paper reports on a series of five chiral Schiff base push‐pull compounds derived from enantiomerically pure (1R,2R)‐(−)‐1,2‐diaminocyclohexane. The NiII, CuII, ZnII and PdII complexes supported by a ferrocene‐containing unsymmetrically‐substituted N2O2 quadridentate Schiff base ligand were prepared via template reactions and isolated in 74–87 % yields. A combination of EA, IR, UV/vis and 1H/13C{1H} NMR spectroscopy, HRMS spectrometry, cyclic voltammetry and single‐crystal X‐ray analysis (for the proligand 2 and its NiII derivative 3), together with computational methods (DFT and TD‐DFT) was used to fully characterize and study the properties of all products. Both 2 and 3 crystallize in the orthorhombic non‐centrosymmetric space group P212121, with two (R,R)‐(−)‐chiral carbon atoms in their structure. Second‐order nonlinear polarizabilities β have been measured by using Harmonic Light Scattering at 1.91 μm, with the Pd(II) species showing the higher NLO response of 460×10−30 esu. [ABSTRACT FROM AUTHOR]

The reaction of trans‐[Pt(DMSO)2MeCl] with 2‐alkylsubstituted pyridines pyR affords a series of complexes of the type [Pt(pyR)(DMSO)MeCl]. These complexes are rare examples of organometallic square‐planar complexes having four different ligands. Of the three possible geometric isomers, only the trans(N,S)‐[Pt(pyR)(DMSO)MeCl] was observed in solution and isolated in the solid state. However, the lack of chirality typical to square planar geometry can be resolved in several ways one of which is described in this paper. 1H NMR studies reveal diastereotopicity of the DMSO methyls, as well as the CH2 protons in the ethyl‐ and neopentyl‐pyridine complexes and the methyls in the isopropyl‐pyridine derivative. This observation can be ascribed to restricted rotations around the Pt−N bond, thus resulting in the presence of planar chirality for these complexes. Additionally, large downfield shifts in the 1H NMR spectra of the α C−H protons in the pyridine substituents suggested the presence of Pt⋯H−C interactions, confirmed via single crystal X‐ray studies in the case of the isopropyl complex [Pt(pyip)(DMSO)MeCl] (4), which shows an apical Pt⋯H interaction with a short 2.585 Å distance. DFT calculations shed light into the stability of these complexes and the influence of the pyridine‐substituent on their chiral configuration. [ABSTRACT FROM AUTHOR]

This paper explores the interaction of divalent [Sm(DippForm)2(thf)2] with substrates containing azo linkages. Treatment of [Sm(DippForm)2(thf)2] with trans‐azobenzene results in formation of mononuclear [Smlll(DippForm)2(Ph2N2)(thf)] ⋅ 3THF (1) or dinuclear [Smlll(DippForm)(Ph2N2)(thf)]2 ⋅ 4THF (2) and [Sm(DippForm)3] depending on the reaction stoichiometry, where azobenzene has undergone either a one or two electron reduction. These reactions parallel the corresponding reactions of [Sm(C5Me5)2(thf)2], but the coordination of [N2Ph2]− in 1 differs significantly from that of {Sm(C5Me5)2(Ph2N2)(thf)}. On the other hand, the structure of 2 is similar to that of the pentamethylcyclopentadienyl analogue. The reaction of [Sm(DippForm)2(thf)2] with 1H‐1,2,3‐benzotriazole also yielded a trivalent samarium complex containing benzotriazolate (btz), [Smlll(DippForm)2(btz)(thf)] ⋅ THF (3), and suggests more utilization of 1H‐1,2,3‐benzotriazole in divalent lanthanoid reduction chemistry is possible. [ABSTRACT FROM AUTHOR]

The key to obtain supercapacitors with high energy density is rational design and synthesis of negative electrode materials. Herein, a new type of polyoxometalate‐based coordination polymer was prepared by one‐step hydrothermal method. Polymer 1 with honeycomb two‐dimensional network structure is beneficial to improve electrical conductivity and storage capacity because of its π‐π stacking interaction. Ti3C2Tx, an MXene material with excellent electrical conductivity, was mixed with compound 1, which has rich redox reactions. As expected, 1@Ti3C2Tx exhibited outstanding specific capacitance (768.7 F g−1 at 8 A g−1), which is superior to many materials. In addition, the hybrid material also showed good cycle stability (88.1 % capacity retention after 1000 cycles). This work provides an effective way to develop hybrid electrode materials based on polyoxometalate‐based coordination polymers as supercapacitors. In addition, using 1@Ti3C2Tx as the negative electrode material and celery leaf carbon paper as the positive electrode material, the asymmetric supercapacitor device is fabricated. When the power density is 629.7 W kg−1, the energy density is 9.2 Wh kg−1, which indicates that it has a good application prospect. [ABSTRACT FROM AUTHOR]

The development of catalytic systems for the oxidation of organic substrates using renewable sources such as water and dioxygen remains challenging. In this paper we report the synthesis and full characterization of a new dyad combining a ruthenium(II)‐based chromophore and a bio‐inspired copper(II) pre‐catalyst. In particular, photo‐induced electron transfer from the photosensitized RuII subunit toward the CuII center is highlighted. The photogenerated CuI moiety proves to be catalytically efficient for sulfides oxidation by 3O2 in the presence of a sacrificial electron source. Finally, the covalent association of the two partners favors Cu/O2‐based catalysis at the expense of a 1O2‐centered reactivity for a bimolecular mixture. [ABSTRACT FROM AUTHOR]

The number of scientific articles that need to be considered to cover a research topic is ever‐increasing and quite difficult for a newcomer to assimilate. This is particularly true in dynamic discipline like Molecular Magnetism. In order to help young researchers in this field, this article proposes a "review of reviews" also known as an "umbrella review" on lanthanide‐based single‐molecule magnets (4 f‐SMM). As a preamble, various bibliographic search techniques and AI‐based tools for bibliographic search, indexing, and summarization are proposed and commented. Then, the main milestones in 4 f‐SMM are identified. In the core of the paper, books, book articles, and reviews dealing with 4 f‐SMM are contextualized and classified by subtopics. This article is therefore proposed as a gateway to the 4 f‐SMM field. [ABSTRACT FROM AUTHOR]

The paper deals with the synthesis of a series of cationic [Pt(ppz)2(N^N)]2+ complexes containing deprotonated 1‐phenyl‐1H‐pyrazole as cyclometallating (C^N) ligands and α‐diimines (N^N) in the form of water‐soluble salts with OTf− (trifluoromethanesulfonate) counter ions. These complexes were obtained from cis‐[Pt(ppz)2Cl2] through chloride ligands substitution with α‐diimines. The complexes were identified by means of NMR spectroscopy and their molecular structures were confirmed by X‐ray crystallography. The photophysical properties of these complexes were studied in detail. These complexes showed strong luminescence in MeOH/EtOH 1 : 1 glasses at 77 K but were almost non‐emitting in MeCN solutions at room temperature. Their emission properties were compared to analogues IrIII complexes. [ABSTRACT FROM AUTHOR]

This paper presents definitive structural evidence for N,P(III)‐monophosphaamidines in P=C and N=C isomeric forms from a combination of new syntheses, single‐crystal X‐ray diffraction (SC‐XRD), solid‐state NMR and FTIR. Evidence is also provided for C‐amino‐(σ2,λ3)‐phosphaalkene and C‐(σ3,λ3)‐phosphinoimine tautomerism in solution using multi‐nuclear NMR methods. Synthesis and SC‐XRD structure determination of a trisubstituted N,N',P(III)‐monophosphaguanidine is presented, the first structure of a phospha(III)guanidine with two ionizable H atoms. The structural evidence is convincing for an N=C geometry, resulting in both N−H and P−H in the molecule. A detailed computational investigation using DFT methods is presented, with the goal of understanding the tautomeric structure preferences both at the fundamental level (parent molecules with all substituents on the heteroatoms being hydrogen) and using the full structures containing the very bulky 2,6‐diisopropylphenyl (Dipp) substituents employed in this study. Arguments are espoused for treating phospha(III)amidines and ‐guanidines as new types of functional groups, similar to but distinct from the familiar organic analogues. Limited reactivity studies and a voltammetry study of one phospha(III)amidine are included with the supporting information. [ABSTRACT FROM AUTHOR]

Chiral nematic mesoporous silica and organosilica have iridescent properties that make them attractive for decoration and sensing. The limited number of commercial organosilica precursors available to create these materials has meant that they have a limited range of chemical and mechanical properties. In this paper, we incorporate vinyl groups in the mesoporous (organo)silica materials and demonstrate their functionalization with thiols through the thiol‐ene click reaction. In this way, we have been able to access chiral nematic mesoporous materials with different functional groups on the surface. We demonstrate that the hydrophobicity of the materials can be tuned, enabling detection of mixtures of organic solvents in water as well as showing promise for ion sequestration. [ABSTRACT FROM AUTHOR]

The aim of the paper was to synthesize Mn/Ca entities that are structurally similar to the reported oxygen‐evolving complex (OEC) of photosystem II (PSII). Here we have ventured Schiff base combinations of racemic (±)‐3‐Aminopropane‐1,2‐diol and Salicyladehyde (H3L1)/o‐Vanillin (H3L2) with varied ratios of ligand : CaIIsalt : MnIIIsalt. Interestingly, H3L2 : CaCl2 : MnCl2 (2 : 1 : 1) afforded [{MnIII2CaII2(HL2)2Cl2(μ3‐OH)2(H2O)6}Cl2 ⋅ 2H2O] (3) whereas H3L1 : CaCl2 : Mn(acetate)2 (2 : 1 : 1) and H3L1 : CaCl2 : MnCl2 (2 : 1 : 2), generated [{MnIV(HL1)2}2 ⋅ 6H2O](1) and [{MnIII3MnII(HL1)3(μ2‐Cl)3(μ3‐O)} ⋅ 2CH3OH ⋅ 2H2O] (2) respectively. More importantly, we have been able to get a structure which offers partial similarity to reported structure of the OEC. Variable temperature magnetic susceptibility measurements have been performed in the 1.8–30 K region for all the compounds. Overall, these studies provide a critical understanding for the rational design and construction of synthetic OEC. [ABSTRACT FROM AUTHOR]

Editor Karen Hindson highlights the exciting new features that readers can look forward to and introduces new board members that will advise the journal in its 20th volume. Editor Karen Hindson highlights the exciting new features that readers can look forward to and introduces new board members that will advise the journal in its 20th volume. [ABSTRACT FROM AUTHOR]

EurJIC is proud to present a bumper issue on Spin‐Crossover Complexes. Our Guest Editors, Keith Murray, Hiroki Oshio and José Antonio Real, have worked hard to put together a fantastic issue. With a valuable personal account of the field by Philipp Gütlich and inspiring papers by leading experts, you will not be disappointed. EurJIC is proud to present a bumper issue on Spin‐Crossover Complexes. Our Guest Editors, Keith Murray, Hiroki Oshio and José Antonio Real, have worked hard to put together a fantastic issue. With a valuable personal account of the field by Philipp Gütlich and inspiring papers by leading experts, you will not be disappointed. [ABSTRACT FROM AUTHOR]

The design of paper products based on copper nanoparticles (NPs) is a challenge because of the intrinsic propensity of Cu to oxidize in contact with air. Here, a comparative study on the growth and chemical stability of Cu NPs in vegetable and bacterial cellulose is described for the first time. Furthermore, comparative studies were performed by using inorganic fillers of distinct dimensionality, Cu NPs and Cu nanowires (NWs), in both types of cellulose. Cu NWs were found to be more resistant to oxidation caused by prolonged air exposure than the Cu NPs. Notably, the cellulosic matrices behave differently for the growth or adsorption of the Cu nanofillers; bacterial cellulose fibers are the most efficient substrate to delay surface oxidation. The data support a role for bacterial cellulose in limiting the oxidation of Cu nanostructures that have been grown or blended in this type of matrix, hence opening up new perspectives for the development of electronic paper technologies that incorporate copper nanophases. [ABSTRACT FROM AUTHOR]