Cu12-Methylsilsesquioxane Cage Decorated with Cu(dppe)2 Moieties for Mild Oxidative Functionalization of Alkanes.

We report a high nuclear (Cu14) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic CuI(dppe)2 moieties and an anionic silsesquioxane cage of an unprecedented CuII12 structural type. The Cu12 cage fragment exhibits a unique (i) combination of Si4-cyclic/Si2-acyclic silsesquioxane ligands and (ii) encapsulation of two different chloride and carbonate species. This complex acts as a promising precatalyst in the mild oxidation and carboxylation of light alkanes to produce alkyl hydroperoxides, alcohols, ketones, or carboxylic acids. The present study widens the family of copper-methylsilsesquioxane clusters with prospective use in oxidation catalysis.

Bimetallic NiCo Metal-Organic Frameworks with High Stability and Performance Toward Electrocatalytic Oxidation of Urea in Seawater.

The urea oxidation reaction (UOR) is an alternative anodic reaction for hydrogen generation via water splitting. The significance of UOR lies in both H2 production and the decontamination of urea-containing wastewater. Commercial electrocatalysts in this field are generally based on noble metals and show several limitations. Bimetal-organic frameworks (BMOFs) can be excellent candidates for the replacement of noble-metal-based catalysts beacuse of their promising features, such as a tunable structure, high surface area, and abundant sites for electrocatalysis. In this study, a series of nickel-cobalt BMOFs (Nix-Coy-BMOFs: x and y refer to a molar fraction of Ni and Co) were synthesized and applied as electrocatalysts in UOR. In particular, a Ni0.15Co0.85-MOF material with a structure similar to that of its parent Co-MOF, revealed exceptional electrocatalytic performance, as evidenced by low values of overpotential (1.33 V vs RHE at 10 mA cm-2), TOF (0.47 s-1), and Tafel slope (125 mV dec-1). At a 40 mA cm-2 current density, Ni0.15Co0.85-MOF also showed excellent stability during the 72 h tests. This performance of NiCo-BMOF can be assigned to the synergistic effect between Co and Ni, abundant active sites, porosity, and a tunable structure, all of which result in an increased reaction rate due to the acceleration of charge and mass transfers. Thus, the present work introduces an efficient noble-metal-free UOR for energy generation from urea-based wastewater.

Multidimensional Hybrid Metal Phosphonate Coordination Networks as Synergistic Anticorrosion Coatings.

In the technologically important field of anticorrosion coatings, it is imperative to form well-defined and characterized films to protect the metal surface from corrosion. Phosphonate-based corrosion mitigation approaches are currently being exploited. Herein, the synergistic action of alkaline-earth metal ions and two carboxy-diphosphonates, PAIBA [N,N-bis(phosphonomethyl)-2-aminoisobutyric acid] and BPMGLY [N,N-bis(phosphonomethyl)glycine], is explored. Also, a family of four novel hybrid metal phosphonate materials is reported, Mg-PAIBA, Ca-PAIBA, Sr-PAIBA, and Sr-Na-PAIBA, whose topological analysis revealed a variety of underlying networks with the 6,10T9, unc, SP 1-periodic net (4,4)(0,2), and unique topologies. The synergistic metal/carboxy-diphosphonate blends were tested for their anticorrosion performance on carbon steel at preselected concentrations (0.1-1.0 mM) and pH values (4.0-6.0). The results showed an enhanced inhibitory performance in the presence of metal cations at higher concentrations. The inhibition of corrosion at pH 5.0 in the presence of BPMGLY, PAIBA, and their combination with Sr2+ was investigated in detail using electrochemical measurements. Enhanced inhibition was achieved with a 1:1 Sr2+/BPMGLY (or PAIBA) binary system. Polarization curves indicated that the system is a "mixed" inhibitor. This study widens the family of carboxyphosphonate coordination polymers, showing their potential as attractive hybrid coatings with anticorrosion performance.

DFT Study on the Mechanisms and Selectivities in Rh (III)-Catalyzed [5 + 1] Annulation of 2-Alkenylanilides and 2-Alkylphenols with Allenyl Acetates.

The mechanisms and regio-, chemo-, and stereoselectivity were theoretically investigated in the Rh(III)-catalyzed [5 + 1] annulation of 2-alkenylanilides and 2-alkylphenols with allenyl acetates. Two different reactants, 2-alkenylanilides and 2-alkylphenols, were selected as model systems in the density functional theory calculations. The obtained theoretical results show that both these reactants exhibit similar steps, namely, (1) N-H/O-H deprotonation and C-H activation, (2) allenyl acetate migratory insertion, (3) ß-oxygen elimination, (4) intramolecular nucleophilic addition of the nitrogen/oxygen-rhodium bond resulting in [5 + 1]-annulation, and (5) protonation with the formation of the desired product and regeneration of the Rh(III) catalyst. The theoretical evidence suggests that the selectivity is determined at the step of allenyl acetate's migratory insertion. Moreover, the regioselectivity is driven by electronic effects, while the interaction energies (C-H···π and C-H···O interactions) play a more imperative role in controlling the stereoselectivity. The obtained theoretical results not only well rationalize the experimental observations but also provide important mechanistic insights for related types of [5 + 1]-annulation reactions.

Alkoxy-Bridged Dicopper(II) Cores Meet Tetracyanonickelate Linkers: Structural, Magnetic, and Theoretical Investigation of Cu/Ni Coordination Polymers.

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2(Hbdea)2Ni(CN)4]n (1) and [Cu2(dmea)2Ni(CN)4]n·nH2O (2), were successfully self-assembled in water by reacting Cu(II) nitrate with H2bdea (N-butyldiethanolamine) and Hdmea (N,N-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)4]2-. These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu2(µ-aminopolyalcoholate)2]2+ is bridged by diamagnetic [Ni(CN)4]2- linkers, resulting in 1D (1) or 2D (2) metal-organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling (J = -602.1 cm-1 for 1 and -151 cm-1 for 2) between Cu(II) ions within the dimers mediated by the µ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.

Silver Coordination Polymers Driven by Adamantoid Blocks for Advanced Antiviral and Antibacterial Biomaterials.

The development of sustainable biomaterials and surfaces to prevent the accumulation and proliferation of viruses and bacteria is highly demanded in healthcare areas. This study describes the assembly and full characterization of two new bioactive silver(I) coordination polymers (CPs) formulated as [Ag(aca)(µ-PTA)]n·5nH2O (1) and [Ag2(µ-ada)(µ3-PTA)2]n·4nH2O (2). These products were generated by exploiting a heteroleptic approach based on the use of two different adamantoid building blocks, namely 1,3,5-triaza-7-phosphaadamantane (PTA) and 1-adamantanecarboxylic (Haca) or 1,3-adamantanedicarboxylic (H2ada) acids, resulting in the assembly of 1D (1) and 3D (2). Antiviral, antibacterial, and antifungal properties of the obtained compounds were investigated in detail, followed by their incorporation as bioactive dopants (1 wt %) into hybrid biopolymers based on acid-hydrolyzed starch polymer (AHSP). The resulting materials, formulated as 1@AHSP and 2@AHSP, also featured (i) an exceptional antiviral activity against herpes simplex virus type 1 and human adenovirus (HAd-5) and (ii) a remarkable antibacterial activity against Gram-negative bacteria. Docking experiments, interaction with human serum albumin, mass spectrometry, and antioxidation studies provided insights into the mechanism of antimicrobial action. By reporting these new silver CPs driven by adamantoid building blocks and the derived starch-based materials, this study endows a facile approach to access biopolymers and interfaces capable of preventing and reducing the proliferation of a broad spectrum of different microorganisms, including bacteria, fungi, and viruses.

Encapsulation of H4SiW12O40 into an Amide-Functionalized MOF: A Highly Efficient Nanocomposite Catalyst for Oxidative Desulfurization of Diesel Fuel.

Production of hydrocarbon fuels containing sulfur in ultralow levels is in high demand and requires the development of novel catalytic systems for oxidative desulfurization (ODS). Herein, a new nanocomposite SiW12@ZSTU-10 catalyst containing H4SiW12O40 (SiW12) encapsulated into a zinc(II) 3D metal-organic framework (MOF) (ZSTU-10) was assembled and characterized. The intricate structure and porosity of ZSTU-10 permit efficient encapsulation of the catalytically active SiW12 cages. The impact of different experimental parameters on the ODS of model oil containing dibenzothiophene as a typical S-based contaminant was evaluated. The SiW12@ZSTU-10 catalyst exhibits remarkable activity with up to 99.8% sulfur removal in 30 min. Kinetic features, trapping tests, and mechanistic studies were also performed. Furthermore, the catalyst offered an outstanding thermal and chemical stability, without apparent leaching and decline in the activity after six cycles. Such an improved catalytic efficiency of SiW12@ZSTU-10 can be assigned to (i) size-matched occupation of the ZSTU-10 pores by SiW12-active species, (ii) prevention of polyoxometalate (POM) leaching from the MOF matrix, (iii) facilitation of the access of S-based substrates to the active sites of SiW12, and (iv) excellent stability and recyclability of the obtained nanocomposite. The preset work widens a family of promising nanocomposite catalysts for improving the desulfurization performance of hybrid POM-MOF catalytic systems.

Theoretical Analysis of a Three-Component Reaction between Two Diazo Compounds and a Hydroxylamine Derivative: Mechanism, Enantioselectivity, and Effect of Cooperative Catalysis.

The mechanism, enantioselectivity, and effect of chiral phosphoric acid (CPA) cocatalyst were investigated by the density functional theory (DFT) for the three-component asymmetric aminohydroxylation between two diazo compounds and a hydroxylamine derivative. This type of cascade process is cooperatively catalyzed by Rh2(OAc)4 and CPA. The obtained results clearly indicate that the first step of the global reaction involves a nucleophilic attack at the nitrogen center of N-hydroxyaniline by rhodium-carbene intermediates producing imines. Subsequently, an enolate intermediate was recognized as the key species generated from the second diazo compound and the leaving benzyl alcohol (BnOH) fragment of the first step and in the presence of the same dirhodium catalyst. Then, the reaction is terminated by the asymmetric Mannich-type addition, delivering the aminohydroxylation products of an S-R conformation with the assistance of chiral phosphoric acid. The distortion/interaction analysis shows that the relative distortions of CPA and the enol play a vital role in the energy ordering of the stereocontrolling transition states (TSs). Furthermore, the influence of different substituents in CPA was fully rationalized by distortion/interaction analysis. This study opens up novel synthetic possibilities and improves the reaction predictability when exploring the related types of cooperatively catalyzed organic transformations.

Coordination Polymers from an Amino-Functionalized Terphenyl-Tetracarboxylate Linker: Structural Multiplicity and Catalytic Properties.

An amino-functionalized terphenyl-tetracarboxylic acid, 2'-amino-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid (H4tpta), was used as an adaptable linker to synthesize, under hydrothermal conditions, eight coordination polymers (CPs). The obtained products were formulated as [Co(µ6-H2tpta)]n (1), [Co(µ3-H2tpta)(2,2'-bipy)]n (2), [M3(µ6-Htpta)2(2,2'-bipy)2]n (M = Mn (3), Cd (4)), [Ni2(µ4-tpta)(phen)2(H2O)4]n (5), [Zn2(µ6-tpta)(phen)2]n (6), {[Zn2(µ6-tpta)(µ-4,4'-bipy)]·H2O}n (7), and [Zn2(µ6-tpta)(µ-H2biim)(H2O)2]n (8), wherein 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy), 1,10-phenanthroline (phen), or 2,2'-biimidazole (H2biim) are present as additional stabilizing ligands. The structural types of 1-8 vary from one-dimensional (1D) (2, 5) and two-dimensional (2D) (3, 4, 6) CPs to three-dimensional (3D) metal-organic frameworks (MOFs) (1, 7, and 8) with a diversity of topologies. The products 1-8 were investigated as catalysts in the Knoevenagel condensation involving aldehydes and active methylene derivatives (malononitrile, ethyl cyanoacetate, or tert-butyl cyanoacetate), leading to high condensation product yields (up to 99%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were investigated. This work broadens the application of H4tpta as a versatile tetracarboxylate linker for the generation of diverse CPs/MOFs.

A Dual-Purpose Ce(III)-Organic Framework with Amine Groups and Open Metal Sites: Third-Order Nonlinear Optical Activity and Catalytic CO2 Fixation.

The present work focuses on the synthesis and properties of a novel multifunctional cerium(III) MOF, [Ce2(data)3(DMF)4]·DMF (data2-: 2,5-diaminoterephthalate), abbreviated as NH2-Ce-MUM-2. Its crystal structure reveals an intricate 3D 4,5-connected framework with a xah topology. This MOF features unique properties, such as open metal sites, presence of free amino groups, and high stability. Two main applications of NH2-Ce-MUM-2 were investigated: (i) as a heterogeneous catalyst in the CO2 fixation into cyclic carbonates and (ii) as a material with third-order nonlinear optical activity. As a model reaction, the cycloaddition of CO2 to propylene oxide to give the corresponding cyclic carbonate was explored under mild conditions, at the atmospheric pressure of carbon dioxide and in the absence of cocatalyst and added solvent. Various reaction parameters were investigated toward optimization and exploration of substrate scope, revealing up to 99% product yields of cyclic carbonate products. Besides, the structure of NH2-Ce-MUM-2 is highly stable, permitting its recyclability and reusability in further catalytic experiments. The significant contributions of free amino groups and open metal sites within this catalyst were particularly considered when proposing a potential mechanism for the reaction. Z-Scan measurements were used to evaluate the nonlinear optical (NLO) properties of NH2-Ce-MUM-2 at various laser intensities. A high two-photon absorption (TPA) under greater incident intensities shows that NH2-Ce-MUM-2 might be applicable in optical switching devices. Besides, the self-focusing effects of NH2-Ce-MUM-2 under various incident intensities were highlighted by the nonlinear index of refraction (n2). By reporting the synthesis and characterization of a novel MOF, along with its highly promising catalytic and NLO behavior, the current study introduces an additional example of multifunctional material into a growing family of metal-organic frameworks.

Fabrication of Cellulose Filters Incorporating Metal-Organic Frameworks for Efficient Nicotine Adsorption from Cigarette Smoke.

To prevent negative effects of smoking, there is constant research on the development of various types of sustainable filter materials, capable of removing toxic compounds present in cigarette smoke. Because of the extraordinary porosity and adsorption properties, metal-organic frameworks (MOFs) represent promising adsorbents for volatile toxic molecules such as nicotine. This study reports new hybrid materials wherein six types of common MOFs of different porosity and particle size are incorporated into sustainable cellulose fiber from bamboo pulp, resulting in a series of cellulose filter samples abbreviated as MOF@CF. The obtained hybrid cellulose filters were fully characterized and investigated in nicotine adsorption from cigarette smoke, using a specially designed experimental setup. The results revealed that the UiO-66@CF material features the best mechanical performance, facile recyclability, and excellent nicotine adsorption efficiency that attains 90% with relative standard deviations lower than 8.80%. This phenomenon may be caused by the large pore size, open metal sites, and high loading of UiO-66 in cellulose filters. Additionally, the high adsorption capacity showed almost 85% removal of nicotine after the third adsorption cycle. The DFT calculation methods allowed further investigation of the nicotine adsorption mechanism, showing that the energy difference between HOMO and LUMO for UiO-66 was the closest to that of nicotine, which further proves the adsorption ability of nicotine by this material. Owing to the flexibility, recyclability, and excellent adsorption performance, the prepared hybrid MOF@CF materials may find prospective applications in nicotine adsorption from cigarette smoke.

Pillared-MOF@NiV-LDH Composite as a Remarkable Electrocatalyst for Water Oxidation.

Oxygen evolution reaction (OER) represents a highly important electrochemical transformation in energy storage and conversion technologies. Considering the low rate of this four-electron half-reaction, there is a demand for efficient, stable, and noble-metal-free electrocatalysts to improve the kinetic and economical parameters. In this work, a new pillared-MOF@NiV-LDH nanocomposite based on a CoII metal-organic framework (pillared-MOF) and heterometallic Ni/V-layered double hydroxide (NiV-LDH) was assembled via a simple protocol, characterized, and explored as an electrocatalyst in OER. A remarkable electrocatalytic efficiency of pillared-MOF@NiV-LDH in 1 M KOH is evidenced by a low overpotential (238 mV at 10 mA cm-2 current density) and a small value of the Tafel slope (62 mV dec-1). These parameters are very close to those of the reference IrO2 electrocatalyst and are superior to the majority of the LDH- and MOF-based systems previously applied for OER. Excellent stability of pillared-MOF@NiV-LDH was confirmed by the chronopotentiometry tests for 70 h and linear-sweep voltammetry after 7000 cycles. Features such as rich electroactive sites, porous structure, high surface area, and synergic effect between pillared-MOF and NiV-LDH are likely responsible for the remarkable electrocatalytic efficiency of this electrocatalyst in OER. Despite prior reports on the application of NiV-LDH in OER, the present study describes the first example where this type of LDH is blended with MOF to generate a nanocomposite material. The interface between the two components of the composite can improve the electronic structure and, in turn, the electrocatalytic behavior. The introduction of this composite paves the way toward the synthesis of other multicomponent materials with potential applications in different energy fields.

Coordination Polymers Constructed from an Adaptable Pyridine-Dicarboxylic Acid Linker: Assembly, Diversity of Structures, and Catalysis.

4,4'-(Pyridine-3,5-diyl)dibenzoic acid (H2pdba) was explored as an adaptable linker for assembling a diversity of new manganese(II), cobalt(II/III), nickel(II), and copper(II) coordination polymers (CPs): [Mn(µ4-pdba)(H2O)]n (1), {[M(µ3-pdba)(phen)]·2H2O}n (M = Co (2), Ni (3)), {[Cu2(µ3-pdba)2(bipy)]·2H2O}n (4), {[Co(µ3-pdba)(bipy)]·2H2O}n (5), [Co2(µ3-pdba)(µ-Hbiim)2(Hbiim)]n (6), and [M(µ4-pdba)(py)]n (M = Co (7), Ni (8)). The CPs were hydrothermally synthesized using metal(II) chloride precursors, H2pdba, and different coligands functioning as crystallization mediators (phen: 1,10-phenanthroline; bipy: 2,2'-bipyridine, H2biim: 2,2'-biimidazole; py: pyridine). Structural networks of 1-8 range from two-dimensional (2D) metal-organic layers (1-3, 5-8) to three-dimensional (3D) metal-organic framework (MOF) (4) and disclose several types of topologies: sql (in 1), hcb (in 2, 3, 5), tfk (in 4), 3,5L66 (in 6), and SP 2-periodic net (6,3)Ia (in 7, 8). Apart from the characterization by standard methods, catalytic potential of the obtained CPs was also screened in the Knoevenagel condensation of benzaldehyde with propanedinitrile to give 2-benzylidenemalononitrile (model reaction). Several reaction parameters were optimized, and the substrate scope was explored, revealing the best catalytic performance for a 3D MOF 4. This catalyst is recyclable and can lead to substituted dinitrile products in up to 99% product yields. The present study widens the use of H2pdba as a still poorly studied linker toward designing novel functional coordination polymers.

Postsynthetic Modification of NU-1000 for Designing a Polyoxometalate-Containing Nanocomposite with Enhanced Third-Order Nonlinear Optical Performance.

For the advancement of laser technologies and optical engineering, various types of new inorganic and organic materials are emerging. Metal-organic frameworks (MOFs) reveal a promising use in nonlinear optics, given the presence of organic linkers, metal cluster nodes, and possible delocalization of π-electron systems. These properties can be further enhanced by the inclusion of solely inorganic materials such as polyoxometalates as prospective low-cost electron-acceptor species. In this study, a novel hybrid nanocomposite, namely, SiW12@NU-1000 composed of SiW12 (H4SiW12O40) and Zr-based MOF (NU-1000), was assembled, completely characterized, and thoroughly investigated in terms of its nonlinear optical (NLO) performance. The third-order NLO behavior of the developed system was assessed by Z-scan measurements using a 532 nm laser. The effect of two-photon absorption and self-focusing was significant in both NU-1000 and SiW12@NU-1000. Experimental studies suggested a much superior NLO performance of SiW12@NU-1000 if compared to that of NU-1000, which can be assigned to the charge-energy transfer between SiW12 and NU-1000. Negligible light scattering, good stability, and facile postsynthetic fabrication method can promote the applicability of the SiW12@NU-1000 nanocomposite for various optoelectronic purposes. This research may thus open new horizons to improve and enhance the NLO performance of MOF-based materials through π-electron delocalization and compositing metal-organic networks with inorganic molecules as electron acceptors, paving the way for the generation of novel types of hybrid materials for prospective NLO applications.

Hybrid composites of lanthanide metal-organic frameworks with epoxy silanes for highly sensitive thermometry.

Post-synthetic modification of metal-organic frameworks (MOFs) and fabrication of hybrid composites are currently hot topics in the development of new functional materials. In this study, a facile and direct approach for coupling of lanthanide MOFs with epoxy silanes was developed, providing an access to a new series of functional composites. Two types of commercially available epoxy silane, namely 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and (3-glycidoxypropyl)methyl diethoxysilane (KH563), were used to modify Ln-BTB MOFs ([Ln(BTB)(H2O)]n·2n(C6H12O); Ln = Tb or Eu0.001Tb0.999; H3BTB = 1,3,5-benzenetrisbenzoic acid) via covalent grafting involving mechanical grinding, epoxide coupling and curing reactions. The fabricated composites (Tb-BTB@ECTMS, Eu0.001Tb0.999-BTB@ECTMS, Tb-BTB@KH563, Eu0.001Tb0.999-BTB@KH563) and their Ln-MOF precursors were fully characterized, including a detailed study of their stability and fluorescence properties. The obtained composites show high thermal and solution stability, under boiling water conditions and in a wide pH range of 1-12. Application of the composites as temperature sensors in the 197-297 K and 273-343 K temperature ranges was explored in detail, revealing a remarkable sensing behavior. For example, Tb-BTB@ECTMS shows a maximum relative sensitivity (Sr) of 6.85% K-1 at 343 K. Eu0.001Tb0.999-BTB@ECTMS represents a white-light emission material with the CIE coordinates (0.3194, 0.3049) that are very close to those of white light, along with good temperature sensing performance and a relative sensitivity of 4.32% K-1 at 297 K. An enhanced performance of the composites in comparison with the parent MOF materials as well as the mechanism of energy transfer were rationalized by DFT calculations. By unveiling a facile and efficient method for improving the stability of luminescent MOFs, via post-synthetic grafting with epoxy silanes, the present study will stimulate further research at the interface of materials chemistry, MOF design, photoluminescence and temperature sensing.

Acetone Factor in the Design of Cu4-, Cu6-, and Cu9-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes.

The present study describes a new feature in the self-assembly of cagelike copperphenylsilsesquioxanes: the strong influence of acetone solvates on cage structure formation. By this simple approach, a series of novel tetra-, hexa-, or nonacoppersilsesquioxanes were isolated and characterized. In addition, several new complexes of Cu4 or Cu6 nuclearity bearing additional nitrogen-based ligands (ethylenediamine, 2,2'-bipyridine, phenanthroline, bathophenanthroline, or neocuproine) were produced. Single-crystal X-ray diffraction studies established molecular architectures of all of the synthesized products. Several coppersilsesquioxanes represent a novel feature of cagelike metallasilsesquioxane (CLMS) in terms of molecular topology. A Cu4-silsesquioxane complex with ethylenediamine (En) ligands was isolated via the unprecedented self-assembly of a partly condensed framework of silsesquioxane ligands, followed by the formation of a sandwich-like cage. Two prismatic Cu6 complexes represent the different conformers─regular and elliptical hexagonal prisms, "cylinders", determined by the different orientations of the coordinated acetone ligands ("shape-switch effect"). A heterometallic Cu4Na4-sandwich-like derivative represents the first example of a metallasilsesquioxane complex with diacetone alcohol ligands formed in situ due to acetone condensation reaction. As a selected example, the compound [(Ph6Si6O11)2Cu4En2]·(acetone)2 was explored in homogeneous oxidation catalysis. It catalyzes the oxidation of alkanes to alkyl hydroperoxides with hydrogen peroxide and the oxidation of alcohols to ketones with tert-butyl hydroperoxide. Radical species take part in the oxidation of alkanes. Besides, [(Ph6Si6O11)2Cu4En2]·(acetone)2 catalyzes the mild oxidative functionalization of gaseous alkanes (ethane, propane, n-butane, and i-butane). Two different model reactions were investigated: (1) the oxidation of gaseous alkanes with hydrogen peroxide to give a mixture of oxygenates (alcohols, ketones, or aldehydes) and (2) the carboxylation of Cn gaseous alkanes with carbon monoxide, water, and potassium peroxodisulfate to give Cn+1 carboxylic acids (main products), along with the corresponding Cn oxygenates. For these reactions, the effects of acid promoter, reaction time, and substrate scope were explored. As expected for free-radical-type reactions, the alkane reactivity follows the trend C2H6 < C3H8 < n-C4H10 < i-C4H10. The highest total product yields were observed in the carboxylation of i-butane (up to 61% based on i-C4H10). The product yields and catalyst turnover numbers (TONs) are remarkable, given an inertness of gaseous alkanes and very mild reaction conditions applied (low pressures, 50-60 °C temperatures).

Therapeutic Potential of a Water-Soluble Silver-Diclofenac Coordination Polymer on 3D Pancreatic Cancer Spheroids.

This work describes the traditional wet and green synthetic approaches, structural features, and extensive bioactivity study for a new coordination polymer [Ag(µ-PTA)(Df)(H2O)]n·3nH2O (1) that bears a silver(I) center, a 1,3,5-triaza-phosphaadamantane (PTA) linker, and a nonsteroidal anti-inflammatory drug, diclofenac (Df-). Compared to cisplatin, compound 1 exhibits both anti-inflammatory properties and very remarkable cytotoxicity toward various cancer cell lines with a high value of selectivity index. Additionally, the 3D model representing human pancreas/duct carcinoma (PANC-1) and human lung adenocarcinoma (A549) was designed and applied as a clear proof of the remarkable therapeutic potential of 1. The obtained experimental data indicate that 1 induces an apoptotic pathway via reactive oxygen species generation, targeting mitochondria due to their membrane depolarization. This study broadens a group of bioactive metal-organic networks and highlights the significant potential of such compounds in developing advanced therapeutic solutions.

Coordination Polymers from Biphenyl-Dicarboxylate Linkers: Synthesis, Structural Diversity, Interpenetration, and Catalytic Properties.

The present work explores two biphenyl-dicarboxylate linkers, 3,3'-dihydroxy-(1,1'-biphenyl)-4,4'-dicarboxylic (H4L1) and 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylic (H4L2) acids, in hydrothermal generation of nine new compounds formulated as [Co2(µ2-H2L1)2(phen)2(H2O)4] (1), [Mn2(µ4-H2L1)2(phen)2]n·4nH2O (2), [Zn(µ2-H2L1)(2,2'-bipy)(H2O)]n (3), [Cd(µ2-H2L1) (2,2'-bipy)(H2O)]n (4), [Mn2(µ2-H2L1)(µ4-H2L1)(µ2-4,4'-bipy)2]n·4nH2O (5), [Zn(µ2-H2L1)(µ2-4,4'-bipy)]n (6), [Zn(µ2-H2L2)(phen)]n (7), [Cd(µ3-H2L2)(phen)]n (8), and [Cu(µ2-H2L2) (µ2-4,4'-bipy)(H2O)]n (9). These coordination polymers (CPs) were generated by reacting a metal(II) chloride, a H4L1 or H4L2 linker, and a crystallization mediator such as 2,2'-bipy (2,2'-bipyridine), 4,4'-bipy (4,4'-bipyridine), or phen (1,10-phenanthroline). The structural types of 1-9 range from molecular dimers (1) to one-dimensional (3, 4, 7) and two-dimensional (8, 9) CPs as well as three-dimensional metal-organic frameworks (2, 5, 6). Their structural, topological, and interpenetration features were underlined, including an identification of unique two- and fivefold 3D + 3D interpenetrated nets in 5 and 6. Phase purity, thermal and luminescence behavior, as well as catalytic activity of the synthesized products were investigated. Particularly, a Zn(II)-based CP 3 acts as an effective and recyclable heterogeneous catalyst for Henry reaction between a model substrate (4-nitrobenzaldehyde) and nitroethane to give ß-nitro alcohol products. For this reaction, various parameters were optimized, followed by the investigation of the substrate scope. By reporting nine new compounds and their structural traits and functional properties, the present work further outspreads a family of CPs constructed from the biphenyl-dicarboxylate H4L1 and H4L2 linkers.

Non-Calcined Layer-Pillared Mn0.5Zn0.5 Bimetallic-Organic Framework as a Promising Electrocatalyst for Oxygen Evolution Reaction.

Electrocatalytic generation of oxygen is of great significance for sustainable, clean, and efficient energy production. Multiple electron transfer in oxygen evolution reaction (OER) and its slow kinetics represent a serious hedge for efficient water splitting, requiring the design and development of advanced electrocatalysts with porous structures, high surface areas, abundant electroactive sites, and low overpotentials. These requisites are common for metal-organic frameworks (MOFs) and derived materials that are promising electrocatalysts for OER. The present work reports on the synthesis and full characterization of a heteroleptic 3D MOF, [Zn2(µ4-odba)2(µ-bpdh)]n·nDMF (Zn-MUM-1), assembled from 4,4'-oxydibenzoic acid and 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (bpdh). Besides, a series of heterometallic MnZn-MUM-1 frameworks (abbreviated as Mn0.5Zn0.5-MUM-1, Mn0.66Zn0.33-MUM-1, and Mn0.33Zn0.66-MUM-1) was also prepared, characterized, and used for the fabrication of working electrodes based on Ni foam (NF), followed by their exploration in OER. These noble-metal-free and robust electrocatalysts are stable and do not require pyrolysis or calcination while exhibiting better electrocatalytic performance than the parent Zn-MUM-1/NF electrode. The experimental results show that the Mn0.5Zn0.5-MUM-1/NF electrocatalyst features the best OER activity with a low overpotential (253 mV at 10 mA cm-2) and Tafel slope (73 mV dec-1) as well as significant stability after 72 h or 6000 cycles. These excellent results are explained by a synergic effect of two different metals present in the Mn-Zn MOF as well as improved charge and ion transfer, conductivity, and stability characteristics. The present study thus widens the application of heterometallic MOFs as prospective and highly efficient electrocatalysts for OER.

Hybrid Silver(I)-Doped Soybean Oil and Potato Starch Biopolymer Films to Combat Bacterial Biofilms.

This study describes the preparation, characterization, and antimicrobial properties of novel hybrid biopolymer materials doped with bioactive silver(I) coordination polymers (bioCPs). Two new bioCPs, [Ag2(µ6-hfa)]n (1) and [Ag2(µ4-nda)(H2O)2]n (2), were assembled from Ag2O and homophthalic (H2hfa) or 2,6-naphthalenedicarboxylic (H2nda) acids as unexplored building blocks. Their structures feature 2D metal-organic and supramolecular networks with 3,6L64 or sql topology. Both compounds act as active antimicrobial agents for producing bioCP-doped biopolymer films based on epoxidized soybean oil acrylate (SBO) or potato starch (PS) as model biopolymer materials with a different rate of degradability and silver release. BioCPs and their hybrid biopolymer films (1@[SBO]n, 2@[SBO]n, 1@[PS]n, and 2@[PS]n) with a very low loading of coordination polymer (0.05-0.5 wt %) show remarkable antimicrobial activity against Staphylococcus aureus and Staphylococcus epidermidis (Gram-positive) and Escherichia coli and Pseudomonas aeruginosa (Gram-negative) bacteria. Biopolymer films also effectively impair the formation of bacterial biofilms, allowing total biofilm inhibition in several cases. By reporting on new bioCPs and biopolymer films obtained from renewable biofeedstocks (soybean oil and PS), this study blends highly important research directions and widens a limited antimicrobial application of bioCPs and derived functional materials. This research thus opens up the perspectives for designing hybrid biopolymer films with outstanding bioactivity against bacterial biofilms.