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In this work, we use a Bayesian optimization (BO) algorithm to sample the space of covalent organic framework (COF) components aimed at the design of COFs with a high hole conductivity. COFs are crystalline, often porous coordination polymers, where organic molecular units—called building blocks (BBs)—are connected by covalent bonds. Even though we limit ourselves here to a space of three-fold symmetric BBs forming two-dimensional COF sheets, their design space is still much too large to be sampled by traditional means through evaluating the properties of each element in this space from first principles. In order to ensure valid BBs, we use a molecular generation algorithm that, by construction, leads to rigid three-fold symmetric molecules. The BO approach then trains two distinct surrogate models for two conductivity properties, level alignment vs a reference electrode and reorganization free energy, which are combined in a fitness function as the objective that evaluates BBs' conductivities. These continuously improving surrogates allow the prediction of a material's properties at a low computational cost. It thus allows us to select promising candidates which, together with candidates that are very different from the molecules already sampled, form the updated training sets of the surrogate models. In the course of 20 such training steps, we find a number of promising candidates, some being only variations on already known motifs and others being completely novel. Finally, we subject the six best such candidates to a computational reverse synthesis analysis to gauge their real-world synthesizability. [ABSTRACT FROM AUTHOR]

The efficient and stable electroluminescence of quantum dots (QDs) is of great importance in their applications in new display technologies. The short service life of blue QDs, however, hinders their development and commercialization. Different mechanisms have been proposed for the destabilization of QDs in electroluminescent processes. Based on real-time time-dependent density functional theory studies on the QD models covered by Z-type ligands (XAc2, X = Cd, Zn, Mg), the structural evolution is simulated to reveal the mechanism of the reduction reactions induced by electron injection. Our simulations reproduce the experimental observations that the reduction reactions occur at the QD–ligand interface, and the reduced Cd atom is almost in a zero valence state. However, different sites are predicted for the reactions in which the surface metal atom of the QD instead of the metal atom in the ligands is reduced. As a result, one of the arms of the chelate ligand leaves the QD, which tends to cause damage to its electroluminescent performance. Our findings contribute to a mechanistic understanding of the reduction reactions that occurred at the QD–ligand interface. [ABSTRACT FROM AUTHOR]

The sluggish oxygen evolution reaction (OER) in overall electrocatalytic water splitting poses a significant challenge in hydrogen production. A series of transition metal phosphides are emerging as promising electrocatalysts, effectively modulating the charge distribution of surrounding atoms for OER. In this study, a highly efficient OER electrocatalyst (CoP-CNR-CNT) was successfully synthesized through the pyrolysis and phosphatization of a Co-doped In-based coordination polymer, specifically InOF-25. This process resulted in evenly dispersed CoP nanoparticles encapsulated in coordination polymer-derived carbon nanoribbons. The synthesized CoP-CNR-CNT demonstrated a competitive OER activity with a smaller overpotential (η10) of 295.7 mV at 10 mA cm-2 and a satisfactory long-term stability compared to the state-of-the-art RuO2 (η10 = 353.7 mV). The high OER activity and stability can be attributed to the high conductivity of the carbon network, the abundance of CoP particles, and the intricate nanostructure of nanoribbons/nanotubes. This work provides valuable insights into the rational design and facile preparation of efficient non-precious metal-based OER electrocatalysts from inorganic–organic coordination polymers, with potential applications in various energy conversion and storage systems. [ABSTRACT FROM AUTHOR]

Cd-doped ZrO2 catalyst has been found to have high selectivity and activity for CO2 hydrogenation to methanol. In this work, density functional theory calculations were carried out to investigate the microscopic mechanism of the reaction. The results show that Cd doping effectively promotes the generation of oxygen vacancies, which significantly activate the CO2 with stable adsorption configurations. Compared with CO2, gaseous H2 adsorption is more difficult, and it is mainly dissociated and adsorbed on the surface as [HCd–HO]* or [HZr–HO]* compact ion pairs, with [HCd–HO]* having the lower energy barrier. The reaction pathways of CO2 to methanol has been investigated, revealing the formate path as the dominated pathway via HCOO* to H2COO* and to H3CO*. The hydrogen anions, HCd* and HZr*, significantly reduce the energy barriers of the reaction. [ABSTRACT FROM AUTHOR]

Cd-doped ZrO2 catalyst has been found to have high selectivity and activity for CO2 hydrogenation to methanol. In this work, density functional theory calculations were carried out to investigate the microscopic mechanism of the reaction. The results show that Cd doping effectively promotes the generation of oxygen vacancies, which significantly activate the CO2 with stable adsorption configurations. Compared with CO2, gaseous H2 adsorption is more difficult, and it is mainly dissociated and adsorbed on the surface as [HCd–HO]* or [HZr–HO]* compact ion pairs, with [HCd–HO]* having the lower energy barrier. The reaction pathways of CO2 to methanol has been investigated, revealing the formate path as the dominated pathway via HCOO* to H2COO* and to H3CO*. The hydrogen anions, HCd* and HZr*, significantly reduce the energy barriers of the reaction. [ABSTRACT FROM AUTHOR]

Selective activation of the C–H bond of aromatic hydrocarbons is significant in synthetic chemistry. However, achieving oriented C–H activation remains challenging due to the poor selectivity of aromatic C–H bonds. Herein, we successfully constructed alternately arranged Au–C4 and Au–O4 organometallic coordination networks through selective aromatic C–H bond activation on Au(111) substrate. The stepwise reaction process of the 5, 12-dibromopyrene 3,4,9, 10-tetracarboxylic dianhydride precursor is monitored by high-resolution scanning tunneling microscopy. Our results show that the gold atoms in C–Au–C organometallic chains play a crucial role in promoting the selective ortho C–H bonds activation and forming Au–C4 coordination structure, which is further demonstrated by a comparative experiment of PTCDA precursor on Au(111). Furthermore, our experiment of 2Br-PTCDA precursor on Cu(111) substrate confirms that copper atoms in C–Cu–C organometallic chains can also assist the formation of Cu–C4 coordination structure. Our results reveal the vital effect of organometallic coordination on selective C–H bond activation of reactants, which holds promising implications for controllable on-surface synthesis. [ABSTRACT FROM AUTHOR]

The "antenna effect" is one of the most important energy transfer modes in lanthanide light-emitting polymers. In this study, novel luminescent nanostructured coordination polymers (Eu–PCP) were synthesized in one step using Eu3+ as the central metal ion and 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) as the organic ligand. The unique "antenna effect" observed between Eu3+ and TCPP leads to a substantial improvement in the electrochemiluminescence (ECL) emission efficiency. Eu–PCP exhibits good cathodic ECL characteristics. Additionally, Au@SnS2 nanosheets exhibit favorable electrical conductivity, biocompatibility, and a significant specific surface area. This makes them a suitable choice as substrate materials for the modification of electrode surfaces and capturing antigens. Being well known, the development of sensitive and rapid methods to detect chloramphenicol is essential for food safety. Based on this, we report a novel competitive electrochemiluminescence immunoassay to achieve ultra-sensitive and highly specific detection of chloramphenicol. The linear range was 0.0002–500 ng mL−1 and the detection limit was 0.09 pg mL−1. Apart from that, the experimental results proved that it provided a new analytical tool for the detection of antibiotic residues in food safety. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Chemical Communications." It includes the ISSN, CODEN, and date of publication. The contents list features various articles and communications on topics such as photocatalytic decarboxylation, visible-light-induced difunctionalization, supramolecular chemical biology, enzymatic approaches for diversifying bioproducts, and more. The journal is published by The Royal Society of Chemistry, a leading chemistry community, and is part of the EES family. It is a registered charity and focuses on exceptional research in solar energy and photovoltaics. [Extracted from the article]

In this work, a novel Fe, Ni bimetallic porous coordination polymers (PCPs) was synthesized, featuring a ligand composed of N, S-rich 6-thioguanine. Through bimetallic synergistic catalysis and self-sulfurization, this bimetallic PCPs transforms into N, S co-doped carbon (NSC)-coated (Fe,Ni) 9 S 8 /Ni 3 S 2 bridged nanowires. Due to N, S co-doped (Fe,Ni) 9 S 8 /Ni 3 S 2 @NSC bridged nanowires, additional electrocatalytic active sites are provided, while the interconnected nanowires simultaneously enhance the overall conductivity of the catalyst. The as-obtained (Fe,Ni) 9 S 8 /Ni 3 S 2 @NSC exhibits excellent OER performance, with an overpotential as low as 252 mV at a current density of 10 mA cm−2. [Display omitted] • In this work, a novel Fe, Ni bimetallic porous coordination polymers (PCPs) was synthesized, featuring a ligand composed of N, S-rich 6-thioguanine. • Through bimetallic synergistic catalysis and self-sulfurization, the bimetallic PCPs transforms into N, S co-doped carbon (NSC)-coated (Fe,Ni) 9 S 8 /Ni 3 S 2 bridged nanowires. • This work indicates that metal sulfides bridged nanowires are an effective method for improving the overall conductivity of electrocatalysts and enhancing electrocatalytic performance. Improving the conductivity of the electrocatalyst itself is essential for enhancing its performance. In this work, N, S-rich 6-thioguanine (TG) is selected as the ligand to synthesize a Fe, Ni bimetallic porous coordination polymer (PCP), which is then derived to fabricate N,S codoped carbon (NSC)-coated (Fe,Ni) 9 S 8 /Ni 3 S 2 bridged nanowires. The (Fe,Ni) 9 S 8 /Ni 3 S 2 @NSC bridged nanowires obtained through bimetallic synergistic catalysis and self-sulfurization processes not only introduced additional electrocatalytic active sites but also significantly enhance the overall conductivity of the catalyst due to the interconnected nanowire structure. The resulting (Fe,Ni) 9 S 8 /Ni 3 S 2 @NSC demonstrates remarkable oxygen evolution reaction (OER) performance, exhibiting an overpotential as low as 252 mV at a current density of 10 mA cm−2. This work proposes a novel strategy for enhancing the overall conductivity of catalysts by growing bridged nanowires, providing valuable insights and inspiration for the design and preparation of advanced transition metal sulfide electrocatalysts. [ABSTRACT FROM AUTHOR]

A facile and in situ successive linker replacement through single-crystal-to-single-crystal (SC--SC) transformation process in cadmium coordination networks (CNs) based on 3,6-bis(pyridin-3-yl)-1,2,4,5-tetrazine (3,3'-pytz) and 4,4'-bipyridine (4,4'-bipy) in chloroform/methanol solution is reported. In this work, we synthesized a 2D square-grid homo-linker (4,4'-bipy) coordination network of {[Cd(4,4'-bipy)2(ClO4)2] (CHCl3)4}n (1) after 24 h at room temperature. Compound 1 undergoes facile and in situ SC--SC transformation at room temperature to a 2D rectangular-grid mixed-linker (4,4'-bipy and 3,3'-pytz) coordination network of {[Cd(4,4'-bipy)(3,3'-pytz)(ClO4)2](CHCl3)(MeOH)}n (2) after two weeks through a core@shell crystal. Further, by keeping compound 2 in the mother liquor, the second SC--SC structural transformation to the 2D rhombic-grid homo-linker (3,3'-pytz) of {[Cd(3,3'-pytz)2(H2O)1.4(MeOH)0.6](3,3'-pytz)(MeOH)1.4(ClO4)2}n (3) occurs within two months. In these stepwise SC--SC transformations, we report for the first time the facile and in situ fabrication of 2D coordination networks by the replacement of linkers via the core--shell pathway. Unlike compound 3, which was stable in air, single crystals of 1 and 2 were unstable outside the mother solution, and due to the absorption of water from air, they were transformed into microcrystalline materials of {[Cd(4,4'-bipy)(H2O)2(ClO4)2](4,4'-bipy)}n (1T) and {[Cd(3,3'-pytz)(H2-O)2(ClO4)2](4,4'-bipy)}n=1 or ∞ (2T), respectively. [ABSTRACT FROM AUTHOR]

Based on crystal engineering, three Zn/Cd-based metal--organic frameworks (MOFs) (FUM-153(Zn--H), FUM-167(Cd--H), and FUM-176(Cd--NH2)) were successfully prepared from rigid O-donor/flexible N-donor linkers (H2bdc (terephthalic acid) (L(O) H) or NH2-H2bdc (2-aminoterephthalic acid) (L(O) NH2) and bpfb (N,N'- 1,4-(phenylene) diisonicotinamide) (L(N))) with Zn/Cd ions. Structurally, the major difference among the FUMs is the various behaviors of the DMF solvent in the lattice or the coordination environment of the structures. This study investigated the effect of hydrogen bonding of NH2 substitution in 2-D layer linkers and its effect on the layer architecture. The results showed that hydrogen bonding indirectly affects the coordination of DMF solvent to the metal center and the porosity. To investigate the effect of the NH2 substitution in the presence or absence of the DMF solvent in the FUMs, the Cambridge Structural Database (CSD) was surveyed for similar structures with the L(O) H and L(O) NH2 linkers. Remarkably, the obtained data suggested that the existence of NH2 substitution may reduce the probability of the coordination of DMF to the metal centers. Theoretical studies were carried out to explore the gas adsorption performance of the title FUMs. A better CH4 adsorption compared to CO2 for all FUMs was observed. It is worth noting that CH4 and CO2 gas adsorption in FUM-176(Cd--NH2) is higher than that in FUM-153(Zn--H) and FUM-167(Cd--H). It can be deduced that the NH2 substitution in 2-D layer linkers prevented the entering of DMF molecules into the framework (lattice or coordinated solvent). Consequently, more accessible pores are provided for gas molecules. The work demonstrates the role of linker functionality in the crystal structure, pore size, and gas adsorption properties. [ABSTRACT FROM AUTHOR]

Two new bis-Schiff base metal(II) complexes viz., bis{N′-[(6-methoxynaphthalen-2-yl)methylidene]-N-methylcarbamohydrazonothioato}-copper(II) complex [Cu(L)2](1) and bis{N′-[(6-methoxynaphthalen-2-yl)methylidene]-N-methylcarbamohydrazonothioato}-nickel(II) complex [Ni(L)2](2), were synthesized and designed from a bidentate-N,S donor Schiff base ligand (HL), and characterized via a single crystal X-ray diffraction (SC-XRD) study, FT-IR, UV-visible and fluorescence spectroscopy, thermal analysis and DFT calculations. Single crystal X-ray diffraction analysis established the perfect square-planar geometry around the metal(II) ions obtained by the coordination of the two N and two S atoms from the two deprotonated HL ligands. Non-covalent intermolecular interactions, which are the main features of the supramolecular assembly, were investigated via Hirshfeld surface (HSs) analysis and 2D-fingerprint plots (FPs) for both the complexes. The supramolecular architecture within the crystal packing is stabilized by C–H⋯S, C–H⋯O and N–H⋯O type hydrogen bonds for the copper(II) complex [Cu(L)2](1), while C–H⋯S, C–H⋯N and N–H⋯O connecting units stabilize the supramolecular assembly for the nickel(II) complex [Ni(L)2](2). The thermal properties of the synthesized complexes offer valuable details on the stability of the complexes. The intermolecular interaction energies have been estimated and their topologies were explored using energy framework analysis. Their interactions with calf-thymus DNA (CT-DNA) and bovine serum albumin (BSA) proteins were also evaluated using UV-visible and fluorescence spectroscopic methods. Absorption titration studies revealed that they interacted strongly with CT-DNA. To gain insight into the potential antiviral applications, we examined the molecular docking of the copper(II) complex [Cu(L)2](1) and nickel(II) complex [Ni(L)2](2) with SARS-CoV-2 RNA binding protein (PDB ID: 6WKP), the Omicron RBD protein (PDB ID: 7WRL) and HIV-1 protease (PDB ID: 8CI7) viruses. They bind to the active positions of viral proteins and show good inhibition performance with target viral proteins. A stronger binding was predicted between the complexes and the SARS-CoV-2 RNA, Omicron and HIV-1 viruses through the negative values of binding affinity. The binding free energies computed using a molecular docking approach were analyzed in detail and the importance of specific interactions was outlined. Furthermore, molecular docking calculations of the complexes against DNA binding protein (PDB ID: 7UV6) were also evaluated. The calculated docking results suggested that they could be adopted as potential inhibitors for the development of new anti-SARS-CoV-2 Omicron and anti-HIV drugs. [ABSTRACT FROM AUTHOR]

A new type of extended viologen, N,N′-2,5-bis(3-pyridinium)thiazolo[5,4-d]thiazole dipropionate, (m-H2TTzPA)(HSO3)2 (1), was synthesized, and two new coordination polymers, {[Cd(m-TTzPA)Br2]·H2O}n (2) and {[Zn(m-TTzPA)Br2]·H2O}n (3), were prepared based on the m-TTzPA ligand. Compounds 1–3 exhibit photochromic behaviors, which were proved using single-crystal X-ray diffraction, UV-vis spectroscopy and EPR characterizations. Furthermore, all the compounds have obvious fluorescence quenching behaviors upon irradiation using a xenon lamp, where compound 1 exhibits a significant quenching efficiency of 95.84%. [ABSTRACT FROM AUTHOR]

A caged metal–organic framework based on heptanuclear and binuclear copper clusters, namely [Cu9(L)10(H2O)2][Me2NH2+]2 (Cu-MOF) (L = rigid 6-(1H-tetrazol-5-yl)-2-naphthoic acid) was synthesized and structurally characterized by a solvothermal method. Single-crystal X-ray diffraction shows that Cu-MOF displays a three-dimensional porous anionic framework and exhibits a cage-cavity structure. The tri-functional ligand uses two coordination modes to bridge different SBUs to form a dodecahedral cage. Since Cu-MOF possesses both anionic and porous frameworks, it could be used for efficient and selective absorption of cationic organic dyes. Further studies truly showed that both the charge and size of the dye molecules affect the absorption of Cu-MOF. Besides, thanks to the electronic configuration and wide range of visible light absorption properties of the heptanuclear copper clusters, Cu-MOF could be used as a photocatalyst for energy transfer from oxygen molecules to singlet oxygen, and successfully oxidized benzyl alcohol to benzoic acid in air under additive-free mild conditions. Therefore, rationally prepared Cu-MOFs, guided by crystal engineering, demonstrate potential for application as organic dye adsorption separators and photocatalysts, and the feasibility of preparing functionally tailored frameworks using tri-functional ligands consisting of tetrazolium and carboxylate acid is presented. [ABSTRACT FROM AUTHOR]

Cobalt and nickel are vital metals for the transition to a decarbonized society, currently in critical supply conditions to meet future demands. The recovery of those metals from secondary sources can mitigate this issue, as well as treating hazardous waste and increasing its economic value. In this work, ionic polymers inspired by deep eutectic solvents (DES) were studied for cobalt and nickel recovery from representative recycling solutions. These polymers were prepared by simple and fast photopolymerization process combining [2-(methacryloyloxy) ethyl] trimethylammonium chloride (METAC) with a series of hydroxylated compounds (e.g. alcohol and phenolic compounds). Different driving forces for metal absorption; ionic interactions, hydrogen bonding coordination, acidity of the media and polymer swelling have been investigated. The poly(METAC:1-butanol) polymer showed the highest absorption capacity (46 ± 5 mg g−1 and 46 ± 4 mg g−1 for cobalt and nickel, respectively), competing with conventional materials. Moreover, the metal stripping and recovery step was investigated. Favourably, deionized water presented the highest desorption efficiency, in comparison with HCl, rendering this process 'greener' and highly cost-effective. Finally, the ionic polymers were successfully reused as absorbents for five absorption/desorption cycles, maintaining structural integrity. This approach can pose an alternative way of using systems inspired by DES, with application at a larger scale upon further optimizations. [ABSTRACT FROM AUTHOR]

The influence of dopant molecules on the structure and functionality of spin-crossover (SCO) materials is surveyed. Two aspects of the topic are well established. Firstly, isomorphous inert metal ion dopants in SCO lattices are a useful probe of the energetics of SCO processes. Secondly, molecular alloys of iron(II)/triazole coordination polymers containing mixtures of ligands were used to tune their spin-transitions towards room temperature. More recent examples of these and related materials are discussed that reveal new insights into these questions. Complexes which are not isomorphous can also be co-crystallised, either as solid solutions of the precursor molecules or as a random distribution of homo- and hetero-leptic centres in a molecular alloy. This could be a powerful method to manipulate SCO functionality. Published molecular alloys show different SCO behaviours, which may or may not include allosteric switching of their chemically distinct metal sites. [ABSTRACT FROM AUTHOR]

Two bidentate ligands (L1 = 1-pentyl-2-(pyridin-2-yl)-1H-benzimidazole and L2 = 1-heptyl-2-(pyridin-2-yl)-1H-benzimidazole) were employed for the synthesis of five mononuclear Fe(II) coordination compounds 1–5 containing perchlorate, tetrafluoroborate and triflate counterions. Single-crystal X-ray diffraction analysis confirmed the expected molecular structures of all the reported compounds, revealing a moderately distorted octahedral geometry of {FeN6} coordination chromophores. All five compounds exhibit thermal spin crossover with T1/2 temperatures allocated above 400 K. The theoretical calculations supported the experimental magnetic investigation and helped to explain the electronic structures of the reported complexes with respect to the occurrence of thermal spin state switching. In addition, compound 4 was employed for the preparation of Langmuir–Blodgett films and fabrication of molecular films using the method of spontaneous evaporation of the subphase. While the formation of Langmuir–Blodgett films was unsuccessful due to the instability of the compound at the water/air interface, the latter technique allowed the formation of molecular films of 4 with well-defined thickness and homogeneity. [ABSTRACT FROM AUTHOR]

Copper (Cu)‐based catalysts have established their unique capability for yielding wide value‐added products from CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O‐containing organic species (squaric acid (H2C4O4) and cyclohexanehexaone (C6O6)). It is revealed that the strength of Cu−O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO2RR. Specifically, the C6O6−Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7 % at −0.6 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4−Cu with an about perfect crystalline structure results in uniformly dispersed Cu‐atoms, showing a notable FE of 65.8 % for C2+ products with enhanced capability of C−C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm−2 at −1.0 VRHE, i.e. is already at the boarder of practical relevance. This study sheds light on the rational design of Cu‐based catalysts for directing the CO2RR reaction pathway. [ABSTRACT FROM AUTHOR]

ABSTRACT Milk, owing to its nutritional value, is a staple commodity in daily life. Ensuring its integrity and authenticity is paramount for researchers and the food industry. To evaluate spoilage and adulteration of milk, we proposed a robust and reliable optical method to guarantee milk quality by utilizing riboflavin as an internal biomarker. By precisely controlling the content of Eu3+, Tb3+, and Gd3+ ions, a two‐dimensional ratiometric luminescence lanthanide coordination polymer (Ln‐CP) with adjustable emission centers was synthesized for the detection of riboflavin (RF), leveraging a Förster resonance energy transfer (FRET) and photoinduced electron transfer (PET) process. This method demonstrates high sensitivity and selectivity towards RF and has been successfully applied to the detection of RF in both milk and calf serum. [ABSTRACT FROM AUTHOR]

Two newly derived coordination polymers of Cu(II) and Co(II), namely {[Cu(μ‐5‐AzIA)(Py)2]⋅[Cu(5‐AzIA)(Py)2(H2O)]}n (CP1) and {[Co(μ‐5‐AzIA)2(Py)4]⋅[Co(5‐AzIA)(Py)2]}n (CP2) (5‐AzIA2− = 5‐azidoisophthalate; Py = pyridine) are synthesized and structurally characterized by single‐crystal X‐ray diffraction (SXRD), powder X‐ray diffraction (PXRD), and Fourier transform infrared data. As evident from thermogravimetric data, CP1 loses coordinated water at 110°C and the final residue reaches at 530°C as CuO; CP2 is stable up to 150°C, and the final residue reaches at 415°C as Co2O3. 5‐AzIA2− serves as both chelating and monodentate carboxylate bridging ligand to the adjacent metal centers (Cu(II) in CP1 and Co(II) in CP2) to construct the CPs. The CPs form eight‐member carboxylato bridging, [M2(RCOO)2], and coordinate with Py rings and assemblage through π‐‐‐π interaction. The magnetic measurements of the CPs show antiferromagnetic super‐exchange properties. Interestingly, CP2 shows field‐induced magnetic ordering at a higher magnetic field at a temperature ̴ 2 K owing to the π•••π stacking between the flagging pyridine moieties. Oxygen evolution reaction (OER) shows excellent catalytic effectiveness of CP2 than CP1 with reference to standard RuO2 catalyst. The comparative catalytic activity of CP1 and CP2 was thoroughly investigated and well supported by Tafel slope, charge‐transfer resistance (Rct), and electrochemically active surface area calculation. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. It includes a cover image and an inside cover image, both with accompanying articles. The document also lists several papers that are featured in the journal, covering topics such as crystal structures, coordination polymers, and the synthesis of various materials. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

Effective adsorption of dye pollutants is essential to preserving human health and life before they are released into the environment. Ionic coordination polymers are considered good candidates for the effective elimination of dye pollutants. In this research, an anionic coordination polymer, {[NH2(CH3)2]2[Cd(μ4-L)]·1.5H2O·0.75DMF}n (1), [L4−: (E)-5,5′-(fumaroylbis(azanediyl))diisophthalate], was prepared and characterized. Structural analysis revealed that each Cd(II) ion was linked to four L4− ligands forming a 3D framework. A 2-fold interpenetrated 3D architecture of the compound was observed with a dia topology due to the large pore of a single framework. Owing to its water stability and anionic skeleton, the removal ability of four dyes with different charges and sizes by the compound was investigated. The compound, maintaining the negative charge density, effectively adsorbed the cationic methylene blue (MB) dye, while the elimination of anionic methyl orange (MO) and Congo red (CR) dyes was not observed owing to electrostatic repulsion. Additionally, the compound displayed size-dependent adsorption as evidenced by its non-adsorption of the cationic rhodamine B (RhB) dye. The compound exhibited a high MB adsorption capacity with a maximum of 689.93 mg g−1. The experimental data agreed well with the Langmuir isotherm model, and the adsorption process could be marked as a pseudo-second-order kinetic model. The MB adsorption of the compound could be attributed to electrostatic interactions due to its anionic framework and weak interactions. [ABSTRACT FROM AUTHOR]

Amphiphilic {[Cd3(L)2(phen)2(H2O)6]·2H2O·2DMF}n (1) (H3L = 1,3,5-benzenetricarboxylic acid and phen = phenanthroline) and hydrophilic [Zn3(L)2(H2O)12]n (2) were obtained via hydrothermal reactions. Compound 1 is less hydrophilic due to its hydrophobic phen ligands. Hydrogen bonds extend along one direction in compound 1 and two directions in compound 2; thus, the hydrogen bond continuity of compound 1 is less than that of compound 2. The proton conduction behaviors of the two compounds as fillers of Nafion composite membranes were studied. The results show that the optimal doping amounts of 1 and 2 are 5% and 3%, respectively, and the proton conductivities of 1/Nafion-5 and 2/Nafion-3 composite membranes are about 29% and 60% higher than the proton conductivity of the pure Nafion membrane, respectively. The relationships between the structures and properties have been explored; the inherent hydrogen bonding chains or networks in the crystal structures as well as the additional continuous hydrogen bonds formed between the hydrophilic groups on the surface of their particles and the –SO3H groups of Nafion can provide more proton transfer pathways. The higher doping amount of compound 1 was attributed to its hydrophobic phen ligand, which can promote its compatibility and interactions with the Nafion membrane and reduce aggregation. [ABSTRACT FROM AUTHOR]

The new homochiral 1D metal–organic coordination polymer {Cu[bdc-(N-MePro)H2O]·0.25H2O}n was synthesized using 2-[(1-methyl- L -prolyl)amino]terephthalic acid, which was obtained for the first time. The unique crystal structure of the new compound was determined using powder X-ray diffraction. The catalytic performance of {Cu[bdc-(N-MePro)H2O]·0.25H2O}n in the asymmetric ring opening reactions of styrene oxide and cyclohexene oxide with aniline was evaluated. [ABSTRACT FROM AUTHOR]

Mixed Br/Cl perovskite nanocrystals (PeNCs) exhibit bright pure‐blue emission benefiting for fulfilling the Rec. 2100 standard. However, phase segregation remains a significant challenge that severely affects the stability and emission spectrum of perovskite light‐emitting diodes (PeLEDs). Here, we demonstrate the optimization of the spacing between polydentate functional groups of polymer ligands to match the surface pattern of CsPbBr1.8Cl1.2 PeNCs, resulting in effective synergistic passivation effect and significant improvements in PeLED performances. The block and alternating copolymers with different inter‐functional group spacing are facilely synthesized as ligands for PeNCs. Surprisingly, block copolymers with a higher functional group density do not match PeNCs, while alternating copolymers enable efficient PeNCs with the high photoluminescence intensity, low non‐radiative recombination rate and high exciton binding energy. Density functional theory calculations clearly confirm the almost perfect match between alternating copolymers and PeNCs. Finally, pure‐blue PeLEDs are achieved with the emission at 467 nm and Commission Internationale de l′Eclairage (CIE) coordinates of (0.131, 0.071), high external quantum efficiency (9.1 %) and record spectral and operational stabilities (~80 mins) in mixed‐halide PeLEDs. Overall, this study contributes to designing the polymer ligands and promoting the development of high‐performance and stable pure‐color PeLEDs towards display applications. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Chemical Communications" published in 2024. It includes articles on various topics such as photocatalysis, Raman imaging, glycosylation, and catalysis. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of articles and authors, allowing library patrons to quickly identify articles of interest for their research. [Extracted from the article]

The need for carbon‐neutralization technologies has prompted significant interest in developing materials for CO2 reduction. Donor–acceptor (D–A) based flexible porous coordination polymers {[Zn(o‐phen)(ndc)].(guest)}n, (guest = anthracene = 1‐Ant, and pyrene = 1‐Pyr) are reported as photocatalysts for CO2RR, yielding higher order CH4 product. Electron‐rich anthracene (Ant) and pyrene (Pyr) guests are confined within nanopores, forming D–A charge transfer (CT) complexes with o‐phen ligand of the host. CT interaction enhances visible light absorption and modulates excitonic properties of the photocatalyst by electronic push‐pull effect (exciton binding energy 87 meV for 1‐Ant and 104 meV for 1‐Pyr). Electron donation capability varies from Pyr to Ant, affecting catalytic properties; 1‐Ant yields 1.24 mmolg−1 of CH4 (0.47 mmolg−1 for 1‐Pyr) with CO as minor product. A mixed‐metal multivariate PCP {[Zn0.55Co0.45(o‐phen)(ndc)].(Ant)}n, (1′‐Ant) prepared based on solid‐solution approach by substituting Zn(II) with redox‐active Co(II) enhances CH4 production (2.79 mmolg−1, ≈94% selectivity). D–A CT complex harvests visible light and channels electrons to Co(II) for CO2RR. In situ DRIFTS and theoretical studies elucidate Co(II) site's role in CO2 binding and stabilizing reaction intermediates. This work underscores guest‐modulated electron transfer in PCPs for tailoring catalytic properties by introducing a redox‐active metal in a multivariate approach. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. It includes a list of papers featured in the issue, covering topics such as the photothermal weak absorption of a crystal, halogen bonding proclivity in cocrystals, and the structure and electrical properties of doped single crystals. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions approved training courses offered by the society. [Extracted from the article]

Two new cyano-bridged coordination polymers, {[Ni(bpe)(H2O)2][Ni(CN)4]·2H2O}n (1) and {[Cu(bpe)(H2O)2][Ni(CN)4]·ethanol}n (2) (bpe = 1,2-bis(4-pyridyl)ethane) were synthesized and characterized. This was part of a study attempting to rationalize the formation of Hofmann coordination polymers over their aqua-derivatives, in which we found that the length of the ligand does not control the outcome of the synthesis. In the initial phase of thermogravimetric analysis, compound 1 lost the guest water molecule while compound 2 lost its guest ethanol. Single crystal X-ray diffraction revealed that both compounds crystallize in P1¯ with similar unit cell parameters. In both compounds, the Ni(II) ion is coordinated with four cyanide–carbon atoms in a square planar geometry and Cu(II) or the second Ni(II) ion adopts a distorted octahedral coordination by two bpe ligands, two bridging cyano groups, and two water molecules. In both structures, chains composed of adjacent [Ni(C12H12N2)(H2O)2]2+ (for 1) or [Cu(C12H12N2)(H2O)2]2+ (for 2) are further linked together via [Ni(CN)4]2− units and extend to generate a two-dimensional framework. The presence of disordered terminal cyanide moieties in 1 could be attributed to a larger volume available to this moiety in the structure of 1. The BET surface areas of the activated phases 1′ of 1 and 2′ of 2 are 28 m2 g−1 and 5 m2 g−1, respectively, and originally, they have no pores to accommodate gas molecules at low pressure (1 atm). 1′ does not adsorb carbon dioxide at 195 K (0.30 mmol g−1), 273 K (0.086 mmol g−1) and 298 K (0.056 mmol g−1), or hydrogen at 77 K, but it shows an affinity to adsorb nitrogen (around 2.5 mmol g−1) at 77 K and water vapor molecules (around 0.95 mmol g−1) at 298 K with typical type-II isotherms. 2′ adsorbs a small quantity of water vapor (around 0.20 mmol g−1) at 298 K and does not adsorb carbon dioxide at 195 K (0.125 mmol g−1), 273 K (0.069 mmol g−1) and 298 K (0.062 mmol g−1), or hydrogen at 77 K, but shows more affinity to adsorb nitrogen (around 1.2 mmol g−1) at 77 K. [ABSTRACT FROM AUTHOR]

Under hydrothermal condition, lactate derivative (R)‐4‐(1‐ carboxyethoxy)‐2‐methylbenzoic acid ((R)‐H2cma) as chiral synthon assembled with 4,4′‐di(1H‐imidazol‐1‐yl)‐1,1′‐biphenyl (4,4'‐dib) and Ni(II) ions to obtain complex {[Ni2((R)‐cma)2(4,4'‐dib)2(H2O)] ⋅ 2H2O}n (HU20‐R). In complex HU20‐R, carboxyl group from lactate unit of (R)‐cma2− anion and coordinating H2O molecule adopt a μ2‐coordination mode to obtain dinuclear [Ni2(CO2)2(H2O)]2+ cluster. (R)‐cma2− anions and Ni(II) ions build single left‐handed (R)‐cma‐Ni‐chain, while 4,4'‐dib ligands are bridged by different Ni(II) centers to form double left‐handed 4,4'‐dib‐Ni‐chain. These helical secondary structures are further connected together to result in an 8‐connected 3D framework. PXRD tests indicated that complex HU20‐R has well hydro‐stability. UV‐vis absorption experiment confirmed that HU20‐R is a semi‐conducting material with strong absorption capacity for ultraviolet‐visible (UV‐vis) light. Additionally, electrochemical experiment revealed that HU20‐R has low impedance and high charge transport capacity. Further test results confirm that HU20‐R has noticeable photo‐catalytic effect in photodegradation of Rhodamine B (RhB) and antiferromagnetic property. [ABSTRACT FROM AUTHOR]

9,9‐bis (diphenylphosphorylphenyl) fluorene (FDPO) and dibenzotetrathienoacene (DBTTA), are synthesized as the neutral and anionic ligands, respectively, to prepare the ErIII coordination polymer [Er(DBTTA)3(FDPO)]n. Based on the intramolecular energy transfer, optical gains at 1.5 µm are demonstrated in [Er(DBTTA)3(FDPO)]n‐doped polymer waveguides under excitations of low‐power light‐emitting diodes (LEDs) instead of laser pumping. A ligand‐sensitization scheme between organic ligands and Er3+ ions under an excitation of an ultraviolet (UV) LED is established. Relative gains of 10.5 and 8.5 dB cm−1 are achieved at 1.53 and 1.55 µm, respectively, on a 1‐cm‐long SU‐8 channel waveguide with a cross‐section of 2 × 3 µm2 and a 1.5‐µm‐thick [Er(DBTTA)3(FDPO)]n‐doped polymethylmethacrylate (PMMA) as upper cladding. The ErIII coordination polymer [Er(DBTTA)3(FDPO)]n can be conveniently integrated with various low‐loss inorganic waveguides to compensate for optical losses in the C‐band window. Moreover, by relying on the intramolecular energy transfer and UV LED top‐pumping technology, it is easy to achieve coupling packaging of erbium‐doped waveguide amplifiers (EDWAs) with pump sources in planar photonic integrated chips, effectively reducing the commercial costs. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry." It includes the titles and authors of various articles published in the journal, covering topics such as the synthesis and reactivity of hydride complexes, sustainable copolymers, and the structure and behavior of various metal complexes. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

The 1D homochiral coordination polymer (CP-1) {[Co(dTMP)(bpe)2(H2O)3]·9H2O}n was constructed by using 2′-deoxy thymidine 5′-monophosphate disodium salt (dTMP·2Na), and auxiliary ligand bpe (1,2-bis(4-pyridyl)ethene) and characterized by single-crystal XRD, PXRD, IR, UV-visible, CD and TGA analyses. Molecular simulations revealed the selective chiral behaviour of CP-1 towards phenylalanine and histidine, as indicated by their higher binding free energies compared to other amino acids. Theoretical parameters were also compared with experimental UV-visible verdicts. Notably, the D -enantiomers of phenylalanine and histidine demonstrated strong bonding abilities and optimal configurations for probing and distinguishing them from their L -counterparts. These findings led to propositions suggesting that the dissimilarities between these D and L amino acid forms and their binding orientations with CP-1 may contribute to alterations in the CD signal. CP-1 exhibited a robust inherent circular dichroism (CD) signal in aqueous solutions, modulated by the presence of specific amino acids, namely D / L phenylalanine and D / L histidine. Leveraging the measurement of CD signal intensity, a sensor capable of detecting unmodified amino acids has been developed. Unlike previously reported approaches that relied on complex chemical reactions between initially CD-silent molecules and probed amino acids, this new method offers a more straightforward means of amplifying the CD signal. Consequently, this change facilitates a more accurate differentiation between the enantiomers of these specific amino acids compared to others. [ABSTRACT FROM AUTHOR]

Eugenol, the major constituent of clove oil, has been explored as an essential natural ingredient for ages owing to its versatile pharmacological properties. However, to date, the coordination chemistry of eugenol derivatives has not been much explored. In the present work, an eugenol-based Schiff base ligand (HL) was synthesized and structurally confirmed through ESI-MS, NMR, and FT-IR spectroscopy studies. Consequently, the N,O-donor chelating ligand HL was coordinated with Cd2+, in the presence of bridging pseudohalides (thiocyanate, SCN−, and dicyanamide, N(CN)2−) to synthesize two luminescent coordination polymers (CPs 1 and 2): [Cd2(L)2(X)2]n (where HL = 4-allyl-2-(((2-(benzylamino)ethyl) imino)methyl)-6-methoxyphenol and Xs are bridging pseudohalides, i.e., SCN− and N(CN)2−) on a Cd-eugenol scaffold. The CPs depicted structural diversity, bulk-phase purity, thermal stability, and the presence of interlayer supramolecular C–H⋯π interactions together with C–H⋯S (for CP 1) and C–H⋯N (for CP 2) interactions. The CPs further exemplified themselves as selective and sensitive 'turn-off' probes towards trinitrophenol (TNP) (quenching efficiency: 82.02% and 83.86% for 1 and 2) among a pool of hazardous nitroaromatic compounds (NACs). Accordingly, 1 and 2 exhibited an ultralow limit of detection (LOD) of 0.29 and 0.15 μM, with high quenching constants (KSV) of 5.91 × 104 and 17.60 × 104 M−1, respectively. In addition, TNP sensing events were evidenced to be recyclable and exhibited fast response (∼31 s, 1, and ∼40 s, 2), which increased its real-world viability. Vapor phase TNP sensing was also accomplished upon drop-casted CP films. Experimental investigations and theoretical DFT study confirmed the cooperative occurrence of RET-IFE-PET-collisional quenching and non-covalent π⋯π stacking as key factors involved in the TNP sensing performance. The competency of 1 and 2 in the detection of TNP from several complex environmental matrices (CEMs), viz. matchstick powder, river and sewage water, and soil specimens, was also established with good recovery (∼66–86% and ∼68–93% for 1 and 2, respectively) and high KSV values (3.90–11.39 × 104 and 6.17–18.79 × 104 M−1 for 1 and 2, respectively). [ABSTRACT FROM AUTHOR]

Turbinaria ornata marine macro-algae (TUN) have been applied as carriers for the metallic zinc/ZnO blended nanoparticles, which were synthesized by implementing the extracted phytochemicals of the algae. The resulting hybrid bio-composite (Zn@ZnO/TUN) was characterized as a potential product of promising antioxidant and antidiabetic characteristics in synergetic studies. The obtained composite demonstrate t6he existing or complex biological active groups related to zinc (Zn-O stretching and tetrahedral Zn coordination) and organic groups (amino, methyl, carboxylic, alkynes, P=O, C-C-O, C=N, and N-O) corresponding to the extracted phytochemicals of algae (polysaccharides, phospholipids, lipids, fucose, and phosphodiester). The assessment of Zn@ZnO/TUN hybrid as an anti-oxidant agent validated excellent effectiveness towards the commonly examined radicals (DPPH (88.2 ± 1.44%), nitric oxide (92.7 ± 1.71%), ABTS (90.5 ± 1.8%), and O2•- (30.6 ± 1.32%), considering the determined performance for the commercially used standard (ascorbic acid). Regarding the antidiabetic properties, the incorporation of Zn@ZnO/TUN inhibits the function and activities of the key oxidizing enzymes, either the commercial forms (α-amylase (88.7 ± 1.3%), α-glucosidase (98.4 ± 1.3%), and amyloglucosidase (97.3 ± 1.4%) or the crude intestinal active forms (α-amylase (66.2 ± 1.4%) and α-glucosidase (95.1 ± 1.5%). This inhibitory effectiveness of Zn@ZnO/TUN is significantly better than the measured performances using commercialized miglitol drugs and slightly better than acarbose. Considering the expense and adverse effects of conventional medications, the synthesized Zn@ZnO/TUN blend could be evaluated as a marketable antidiabetic and antioxidant medication. The findings also demonstrate the influence of the derived phytochemicals from Turbinaria ornata and the incorporation of its algae residuals as carriers for the metal nanoparticles on the biological function of the composite. The cytotoxicity investigation reflected safety effect of the composite on colorectal fibroblast cells (CCD-18Co) (96.3% cell viability) and inhibition effect on cancerous colorectal cells (HCT-116) (47.3% cell viability). [ABSTRACT FROM AUTHOR]

ABSTRACT The coordination polymer {[Cu6(CN)6]·HPD}n, CP1; (HPD = heptane‐1,7‐diamine) was prepared and characterized by single‐crystal and powder X‐ray diffraction, UV–Vis spectroscopy, electron microscopy (TEM and SEM), and elemental analyses. The copper atoms are coordinated by C ≡ N ligands, and both exhibit tetrahedral geometry. Cu1 and Cu2 create the pretty unique cluster structure of two quadruple [Cu2(μ3‐CN)2] units exhibiting coprophilic interaction. The building blocks [Cu3(CN)3]2 form fused distorted rectangular rings surrounded with the [Cu2(μ3‐CN)2] motifs exhibiting wide voids to accommodate the guest HPD. The structure of 1 indicates the formation of channels with dimensions 5.121–8.469 Ǻ which extend three‐dimensionally creating fused cavity morphology with different shapes. CP1 was utilized as an efficient sensor for selective quantitative estimation of metal ions (Co2+) and explosives (NB). Advanced oxidation process (AOP) was used as an efficient photocatalyst for the removal of the antibiotic meloxicam (MEL) utilizing AOP in the presence of H2O2 as an oxidant. Scavenge experiments, reusability of catalyst 1, and mechanism of oxidation were also discussed. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. It includes a cover image by Gonzalo Campillo-Alvarado and an inside cover image by Shuai Wang and Xiaoyang Dai. The highlighted articles in this issue include one on multiple synthesis routes for atomically precise noble metal nanoclusters by Lizhong He and Tingting Dong, and another on co-crystal formation versus boron coordination in azopyridines by Jesus Daniel Loya, Sidhaesh A. Agarwal, Nicholas Lutz, Eric W. Reinheimer, and Gonzalo Campillo-Alvarado. The document also mentions professional development opportunities and provides a list of papers featured in the journal. [Extracted from the article]

Three new nonporous mercury(II) coordination polymers (CPs) containing the ditopic 1,1′-(1,4-phenylene)bis(3-(pyridin-4-yl)urea) ligand (4,4-pbubp), namely, {[Hg(4,4-pbubp)Cl2](DMSO)3}n (CP1), {[Hg(4,4-pbubp)Br2](DMSO)3}n (CP2) and {[Hg(4,4-pbubp)I2](DMSO)4}n (CP3) were synthesized and characterized structurally through infrared analysis, elemental analysis (CHNS), TGA, PXRD and single-crystal X-ray diffraction analysis. All of these compounds formed 1D polymeric zigzag chains self-assembled in the crystal into higher-dimensional structures through various hydrogen-bonding interactions involving the urea functional group and several DMSO solvent molecules. These CPs were examined as potential adsorbents for the reversible uptake of iodine from the solution. Theoretical analysis of the adsorption kinetics and isotherms was applied to examine the iodine adsorption data. The results correlated effectively with the pseudo-second-order kinetic model and the Freundlich isotherm model. Our results showed that in this family, the iodine uptake capacity was dependent on the anion (CP1 > CP2 > CP3), and the compound which contained chloride anions (CP1) showed the highest capacity to remove iodine. The maximum uptake capacity of 262.01 mg g−1 iodine over CP1 at room temperature based on the Freundlich model was achieved. After iodine adsorption, compounds@I2 were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDAX) as well as Raman spectroscopy. [ABSTRACT FROM AUTHOR]

The detection of excess toxic anions or cations in an aqueous solution through various fluorescent materials such as organic or inorganic fluorescent materials has aroused significant interest recently. Herein, a new tetraimidazole ligand 1,3-bis(1-imidazolyl)-5-[3,5-bis(1-imidazolyl)-phenoxymethyl]-benzene (timpb) and its two Cd(II) metal–organic frameworks {[Cd2(1,4-bdc)2(timpb)]·5.5(H2O)}n (1) (1,4-benzenedicarboxylic acid = 1,4-H2bdc) and {[Cd2(4,4′-bpdb)2(timpb)]·(MeCN)·2.5(H2O)}n (2) (4,4′-biphenyldicarboxylic acid = 4,4′-H2bpdb) were synthesized. Through X-ray single crystal diffraction analysis, 1 can be considered as a 2-fold interpenetrating pillared-bilayer framework formed by linking [Cd2(1,4-bdc)4]n layers with pairs of timpb ligands, whereas 2 exhibits a 2-fold interpenetrating 3D honeycombed framework formed by linking [Cd(4,4′-bpdb)]n chains with timpb ligands. The solid-state luminescent properties of timpb, 1 and 2 at ambient temperature were also investigated. Moreover, timpb acted as a potential luminescent sensor for the detection of cations Fe3+ or Cu2+ and the anion Cr2O72−, whereas 1 displayed high sensitivity toward the cation Fe3+ and anion Cr2O72−. [ABSTRACT FROM AUTHOR]

This review highlights the most recent applications of Cd(II)-carboxylate-based coordination polymers (Cd(II)-CBCPs), such as sensors, catalysts, and storage materials, in comparison with those of Zn(II) counterparts. A wide range of species with luminescence properties were designed by using proper organic fluorophores, especially a carboxylate bridging ligand combined with an ancillary N-donor species, both with a rigid structure. These characteristics, combined with the arrangement in Cd(II)-CBCPs' structure and the intermolecular interaction, enable the sensing behavior of a plethora of various inorganic and organic pollutants. In addition, the Lewis acid behavior of Cd(II) was investigated either in developing valuable heterogeneous catalysts in acetalization, cyanosilylation, Henry or Strecker reactions, Knoevenagel condensation, or dyes or drug elimination from wastewater through photocatalysis. Furthermore, the pores structure of such derivatives induced the ability of some species to store gases or toxic dyes. Applications such as in herbicides, antibacterials, and electronic devices are also described together with their ability to generate nano-CdO species. [ABSTRACT FROM AUTHOR]

We report herein a versatile method for synthesis of nickel-based inorganic compounds (i.e., Ni–O, Ni–S, Ni–Se, and Ni–P) from one basic nickel-cyanide-bridged coordination polymer (Ni-CP) flakes via a straightforward one-step annealing operation. Thus obtained Ni-based cocatalysts have been loaded over TiO 2 via facile incipient impregnation method to investigate performance towards H 2 production via H 2 O splitting reaction. Among examined compounds, the optimized 0.5Ni-P@TiO 2 exhibited the best photocatalytic activity with a hydrogen generation rate of 7.32 mmol h−1 g−1 compared with pristine TiO 2 (0.086 mmol h−1 g−1). While the 4Ni–Se@TiO 2 has revealed the strongest durability with cumulative hydrogen amount of 48.6 mmol g−1 upon a 5-h reaction, which is 81-fold higher than TiO 2 at identical conditions. On the other hand, Ni–S, Ni–P, and Ni–O, impregnated with 0.5 wt% of titania, show 13, 46, and 49-fold enhancement in evolved H 2 amount higher than the bare titanium dioxide. Additionally, the mixtures have been investigated again through photo-electrochemical measurements confirming the outperforming performance of Ni–P@TiO 2 (0.5% wt). The processed synthesis methodology is economical and easy opening a door to synthesizing various transition metal compound/semiconductor composites for efficient water photocatalytic hydrogen generation. [Display omitted] • Hydrogen extracted from water considered as a future fuel because of its sustainability and cleanliness. • The problem of huge energy required to split H–OH bond in water can be overcome through. • Among several approaches to produce green hydrogen from water, photocatalysis is the completely sustainable and eco-friendly approach. • Herein, we synthesized four nickel compounds from one parent Ni-CP, and investigated their influence on titania photocatalytic properties via water-splitting reaction. • 0.5Ni-P@TiO 2 composite provided the highest HGR (7.3 mmol h−1 g−1) with excellent electrical characteristics, while 4Ni–Se@TiO 2 composite gave the highest cumulative H 2 amount (48.6 mmol g−1), which indicated its distinguished stability. [ABSTRACT FROM AUTHOR]

Bio‐active ethylcellulose (EC) polymeric films have been obtained by incorporating curcumin (curc) and Ag(I)‐based compounds, known for their antioxidant and antimicrobial activity, respectively, within the polymeric matrix. The recently reported Ag(I) coordination polymer, in both its structural forms (α‐[(bpy)Ag(OTf)]∞ and β‐{[(bpy)Ag][OTf]}∞), and the [(bpy)Ag(OTf)]∞‐curc polymeric co‐crystal (bpy=2,2′‐bipyridine; OTf=trifluoromethanesulfonate) have been selected as Ag(I) species. The hybrid composite films have been prepared through the simple solvent casting method and characterized through Powder X‐Ray Diffraction (PXRD), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), UV‐vis spectroscopy. The deep investigation of the film samples highlighted the non‐inert behaviour of EC towards these specific active ingredients. Antimicrobial tests showed that EC films embedding the Ag(I)‐based compounds present good antimicrobial performance, in particular against Staphylococcus aureus, used as a model of Gram‐positive bacteria. In addition, Silver migration tests, performed on the Ag(I)‐incorporating EC films, evidenced low values of silver release particularly in the case of the EC films incorporating [(bpy)Ag(OTf)]∞‐curc. [ABSTRACT FROM AUTHOR]

Two dinuclear double oxygen-bridged iron(III) complexes made of the Fe2(μ2-OR)2 diamond-core cluster resulting from the coordination between iron(III) cations with calix[4]arene ligands and bearing two lower-rim-appended salicylideneamine (4) or o-methoxy-salicylideneamine coordinating sites (5), connected to the macrocyclic platform via three methylene bridges and displaying a salen-type coordination pocket, were synthesized and characterized using single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), high-resolution mass spectrometry (HRESI-MS), IR, TG-DSC and EA techniques. Independent of the presence of the o-methoxy group in the salicylideneamine moieties, the as-formed complexes contained two nonequivalent iron(III) atoms, both adopting a distorted octahedral coordination N2O4-environment but differing in the cis and trans positions of the nitrogen atoms within the metal coordination sphere, as attested by single-crystal X-ray diffraction and DFT-B3LYP calculations. The possible reason for the observed coordination mode of the macrocyclic ligands is their conformational behavior upon coordination with Fe(III) cations, as confirmed by DFT-B3LYP analysis. 57Fe Mössbauer spectroscopy study showed that both Fe(III) atoms were present in high spin states at room temperature and at 80 K in the studied coordination compounds. The methoxy groups located at the ortho position of the salicylideneamine coordinating fragments were observed to influence the energy of the frontier orbitals, resulting in an increase in the bandgap energy from 1.97 eV to 2.07 eV, as experimentally established by solid-state voltammetry study of 42-Fe2 exp and 52-Fe2 exp, respectively. The interplay between the steric and electronic factors, emerging from the o-methoxy group within coordinating salicylideneamine moieties, seemed to have a negligible effect on the electronic properties of the prepared clusters but significantly impacted the frontier orbital energy distribution, according to both experimental data and theoretical calculations. [ABSTRACT FROM AUTHOR]

Although organometallic porous polymer networks are recognized as promising heterogeneous catalysts, the relationship between ligand/monomer geometry and network parameters is usually not well understood due to the lack of atom-resolved characterization methods for the amorphous network matrix. In this work, a series of copper(II) salen-type metal complexes was synthesized, using trans- and cis-1,2-diaminocyclohexane segments, and thoroughly characterized by single-crystal X-ray diffraction and solution- and solid-state NMR spectroscopy. Terminal ethynyl groups of the complexes were then transformed into polyacetylene chains by coordination chain-growth homopolymerization, resulting in highly porous (458–655 m2 g−1) organometallic polymer networks with a copper(II) ion content of about 12 wt%. The presence of paramagnetic copper(II) moieties in these complexes and respective polymer networks required the application of tailored NMR techniques, which together with X-ray crystallography and DFT calculations of the paramagnetic NMR shifts made it possible to investigate the differences in the complex geometry in liquid, powder and crystalline form and compare it with the complex geometry in polymer networks. All prepared organometallic polymer networks were also tested as heterogeneous catalysts for styrene oxidation with uncommonly high substrate conversions and compared with their low-molecular-weight analogues. The high reusability of such heterogeneous polymer-based catalysts was also proven. [ABSTRACT FROM AUTHOR]

Porous molecular crystals (PMCs) have gained significant importance as next-generation functional porous materials. However, the selective crystallisation of the PMC phase remains a challenge. Herein, we have systematically controlled the stability of the luminescent PMC phase prepared using the luminescent Pt(II) complex [Pt(pbim)(N^O)] (pbim = 2-phenylbenzimidazolate, N^O = N-heteroaryl carboxylate) with Pt⋯Pt electronic interactions. The PMC phase formation varied significantly among the complexes depending on the heteroaryl group of the ancillary N^O ligand; the oxazolyl-bearing complex did not form a PMC phase, whereas the pyrazyl- and 5-fluoropyridyl-bearing complexes spontaneously formed a porous structure. This difference was rationalised by the π-stacking capability of the heteroaryl group of the ancillary ligand. Furthermore, owing to the presence of the one-dimensional Pt⋯Pt chains in this PMC phase, the photophysical properties of PMCs resulting from the Pt⋯Pt interactions were also significantly changed by the ancillary ligands. [ABSTRACT FROM AUTHOR]

In this work, we report on five novel coordination polymers (CPs) based on the linkage of the [Cd(6apic)2] building block [where 6apic = 6-aminopicolinate] by different bipyridine-type organic spacers, forming different coordination compounds with the following formulae: [Cd(μ-6apic)2]n (1), {[Cd(6apic)2(μ-bipy)]·H2O}n (2), {[Cd(6apic)2(μ-bpe)]·2H2O}n (3), [Cd(6apic)(μ-6apic)(μ-bpa)0.5]n (4) and {[Cd2(6apic)4(μ-tmbp)]·7H2O}n (5) [where bipy = 4,4′-bipyridine, bpe = 1,2-di(4-pyridyl)ethylene, bpa = 1,2-di(4-pyridyl)ethane (bpa) and tmbp = 1,3-di(4-pyridyl)propane]. Most of the synthesized compounds form infinite metal–organic rods through the linkage of the building block by the bipyridine-type linker, except in the case of compound 4 whose assembly forms a densely packed 3D architecture. All compounds were fully characterized and their photoluminescence properties were studied experimentally and computationally through density functional theory (DFT) calculations. All compounds display, upon UV excitation, a similar blue emission of variable intensity depending on the linker employed for the connection of the building units, among which compound 2 deserves to be highlighted for its room temperature phosphorescence (RTP) with an emission lifetime of 32 ms that extends to 79 ms at low temperature. These good photoluminescence properties, in addition to its stability in water over a wide pH range (between 2 and 10), motivated us to study compound 2 as a sensor for the detection of metal ions in water, and it showed high sensitivity to Fe3+ through a fluorescence turn-off mechanism and an unspecific turn-on response to Zn2+. Furthermore, the compound is processed as a paper-based analytical device (PAD) in which the phosphorescence emission is preserved, improving the sensing capacity toward Fe3+ ions. [ABSTRACT FROM AUTHOR]

The addition of tartrate, oxalate and citrate anions during the one-pot synthesis of 12-MC-4 metallacrown based on β-alaninehydroximate ligands leads, respectively, to dimeric complex Cu10(β-alaha)8 (tartrate)2·10H2O (1) and two one-dimensional coordination polymers, Cu5(β-alaha)4Cu(oxalate)2·8H2O (2) and Cu10(β-alaha)8Cu(citrate)2·19H2O (3). According to X-ray diffraction data for 2 and 3, in the presence of oxalate and citrate anions, infinite chains containing alternating molecules of cationic copper (II) 12 –MC-4 metallacrown and polycarboxylate cuprate anion are formed in crystals. The distance between the metallacrown molecules in the crystal depends significantly on the choice of the initial polycarboxylate anion. In contrast to the oxalate and citrate anions, the dibasic tartrate guest anion does not lead to the formation of endless one-dimensional chains in the crystal. In this case, dimeric complex 1 is formed, for which short Cu–O contacts occur between neighboring 12-MC-4 metallamacrocycles. [ABSTRACT FROM AUTHOR]

Pyridine-alkoxide (pyalk) ligands that support transition metals have been studied for their use in electrocatalytic applications. Herein, we used the pyalk proligands diphenyl(pyridin-2-yl)methanol ([H]PhPyalk, L1), 1-(pyren-1-yl)-1-(pyridin-2-yl)ethan-1-ol ([H]PyrPyalk, L2), 1-(pyridine-2-yl)-1-(thiophen-2-yl)ethan-1-ol ([H]ThioPyalk, L3), and 1-(ferrocenyl)-1-(pyridin-2-yl)ethan-1-ol ([H]FePyalk, L4) to synthesize CuII complexes that vary in nuclearity and secondary coordination sphere. Also, the proligand 1-(ferrocenyl)-1-(5-methoxy-pyridin-2-yl)ethan-1-ol ([H]FeOMePyalk, L5) was synthesized with a methoxy substituted pyridine; however, the isolation of a CuII complex ligated by L5 was not possible. Under variable reaction conditions, the pyalk ligands reacted with CuII precursors and formed either mononuclear or dinuclear CuII complexes depending on the amount of ligand added. The resulting complexes were characterized by single crystal X-ray diffraction, elemental analysis, and cyclic voltammetry. [ABSTRACT FROM AUTHOR]

To foster student's research acumen and innovative abilities, and to deepen their comprehension of inorganic cluster compounds and fluorescent properties, a comprehensive experiment focusing on the synthesis of a cuprous iodide coordination polymer and its application in fluorescent detection of nitrites is designed. This experiment employs a nano-precipitation technique for the preparation of cuprous iodide coordination polymer. Various analytical methods, including Fourier transform infrared (FTIR), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), UV-visible spectrophotometry, and fluorescence spectrophotometer, were utilized to characterize the material's structure and properties. The investigation into the polymer's fluorescence in detecting nitrites revealed high selectivity and sensitivity, with a detection limit of 3.73 µmol∙L-1, positioning the material as a viable "on-off" fluorescence probe for nitrite detection. Through this experiment, students can not only gain the deeper understanding of the structure of cluster polymers and the frontiers of fluorescence detection, but also learn the fundamental knowledge and operational skills in analytical instruments like UV-visible spectrophotometer, fluorescence spectrophotometer. This groundwork is essential for their future engagement in scientific research and related professional activities. [ABSTRACT FROM AUTHOR]

Four lanthanoid anilate coordination polymers (CPs) were synthesised using fluoranilate and chloranilate ligands with La(III), Eu(III) and Dy(III), and PPh4+ as the countercation. The presence of the PPh4+ countercation had a structure directing effect on the CP topology, with a 3D diamondoid (dia) network obtained with La(III) whilst 2D square grid (sql) networks were obtained with Eu(III) and Dy(III). This work represents the first use of fluoranilate in lanthanoid anilate CPs. The additional hydrogen bonding sites afforded by the fluorine substituent influences the packing of the crystal structure whilst the variation in lanthanoid ion size helps determine the topology of the CP. [ABSTRACT FROM AUTHOR]