Mild Microfluidic Approaches to Oxide Nanoparticles Synthesis.

Oxide nanoparticles (oxide NPs) are advanced materials with a wide variety of applications in different fields. The use of continuous flow methods is particularly appealing for their synthesis due to the high control achieved over the reaction conditions and the easy process scalability. The present review focuses on the preparation of oxide NPs using microfluidic setups at low temperature (≤80 °C), since the employment of mild reaction conditions is crucial for developing sustainable and cost-effective processes. A particular emphasis will be put on the improvement over the final product features (e. g., size, shape, and size distribution) given by flow methods with respect to conventional batch procedures. The main issues that arise by treating NPs suspensions in microfluidic systems are product deposition or channel clogging; mitigation strategies to overcome these drawbacks will also be presented and discussed.

Enzyme-like Supramolecular Iridium Catalysis Enabling C-H Bond Borylation of Pyridines with meta-Selectivity.

The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are found via trial-and-error screening due to the low association constants between the substrate and the catalyst in which small stereo-electronic modifications within them can lead to very different reactivities. To circumvent these limitations and to increase the level of reactivity prediction in these important reactions, we report herein a supramolecular catalyst harnessing Zn⋅⋅⋅N interactions that binds to pyridine-like substrates as tight as it can be found in some enzymes. The distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta-selective iridium-catalyzed C-H bond borylations with enzymatic Michaelis-Menten kinetics, besides unique substrate selectivity and dormant reactivity patterns.

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands.

The reactivity of the shortened salen-type ligands H3salmp, H2salmen and H2sal(p-X)ben with variable para-substituent on the central aromatic ring (X = tBu, Me, H, F, Cl, CF3, NO2) towards the trivalent metal ions manganese(III) and iron(III) is presented. The selective formation of the dinuclear complexes [M2(µ-salmp)2], M = Mn (1a), Fe (2a), [M2(µ-salmen)2(µ-OR)2)], R = Et, Me, H and M = Mn (3a-c) or Fe (4a-c), and (M2(µ-sal[p-X]ben)2(µ-OMe)2), X = tBu, Me, H, F, Cl, CF3, NO2 and M = Mn (5a-g) or Fe (6a-g), could be identified by reaction of the Schiff bases with metal salts and the base NEt3, and their characterization through elemental analysis, infrared spectroscopy, mass spectrometry and single-crystal X-ray diffraction of 2a·2AcOEt, 2a·2CH3CN and 3c·2DMF was performed. In the case of iron(III) and H3salmp, when using NaOH as a base instead of NEt3, the dinuclear complexes [Fe2(µ-salmp)(µ-OR)(salim)2], R = Me, H (2b,c) could be isolated and spectroscopically characterized, including the crystal structure of 2b·1.5H2O, which showed that rupture of one salmp3- to two coordinated salim- ligands and release of one salH molecule occurred. The same hydrolytic tendency could be identified with sal(p-X)ben ligands in the case of iron(III) also by using NEt3 or upon standing in solution, while manganese(III) did not promote such a C-N bond breakage. Cyclic voltammetry studies were performed for 3b, 4b, 5a and 6a, revealing that the iron(III) complexes can be irreversibly reduced to the mixed-valence FeIIFeIII and FeII2 dinuclear species, while the manganese(III) derivatives can be reversibly oxidized to either the mixed-valence MnIIIMnIV or to the MnIV2 dinuclear species. The super-exchange interaction between the metal centers, mediated by the bridging ligands, resulted in being antiferromagnetic (AFM) for the selected dinuclear compounds 3b, 4b, 5a, 5e,5f, 6a and 6e. The coupling constants J (-2JS1·S2 formalism) had values around -13 cm-1 for manganese(III) compounds, among the largest AFM coupling constants reported so far for dinuclear MnIII2 derivatives, while values between -3 and -10 cm-1 were obtained for iron(III) compounds.

A Supramolecular Palladium Catalyst Displaying Substrate Selectivity by Remote Control.

Inspired by enzymes such as cytochrome P-450, the study of the reactivity of metalloporphyrins continues to attract major interest in the field of homogeneous catalysis. However, little is known about benefitting from the substrate-recognition properties of porphyrins containing additional, catalytically relevant active sites. Herein, such an approach is introduced by using supramolecular ligands derived from metalloporphyrins customized with rigid, palladium-coordinating nitrile groups. According to different studies (NMR and UV/Vis spectroscopy, XRD, control experiments), the supramolecular ligands are able to accommodate pyridine derivatives as substrates inside the porphyrin pocket while the reactivity occurs at the peripheral side. By simply tuning a remote metal center, different binding events result in different catalyst reactivity, and this enzyme-like feature leads to high degrees of substrate selectivity in representative palladium-catalyzed Suzuki-Miyaura reactions.

Indoles from Alkynes and Aryl Azides: Scope and Theoretical Assessment of Ruthenium Porphyrin-Catalyzed Reactions.

A symbiotic experimental/computational study analyzed the Ru(TPP)(NAr)2 -catalyzed one-pot formation of indoles from alkynes and aryl azides. Thirty different C3 -substituted indoles were synthesized and the best performance, in term of yields and regioselectivities, was observed when reacting ArC≡CH alkynes with 3,5-(EWG)2 C6 H3 N3 azides, whereas the reaction was less efficient when using electron-rich aryl azides. A DFT analysis describes the reaction mechanism in terms of the energy costs and orbital/electronic evolutions; the limited reactivity of electron-rich azides was also justified. In summary, PhC≡CH alkyne interacts with one NAr imido ligand of Ru(TPP)(NAr)2 to give a residually dangling C(Ph) group, which, by coupling with a C(H) unit of the N-aryl substituent, forms a 5+6 bicyclic molecule. In the process, two subsequent spin changes allow inverting the conformation of the sp2 C(Ph) atom and its consequent electrophilic-like attack to the aromatic ring. The bicycle isomerizes to indole via a two-step outer sphere H-migration. Eventually, a 'Ru(TPP)(NAr)' mono-imido active catalyst is reformed after each azide/alkyne reaction.

Concentration-Independent Stereodynamic g-Probe for Chiroptical Enantiomeric Excess Determination.

Enantiomeric excess (ee) determination is crucial in many aspects of science, from synthesis to materials. Within this subject, coupling molecular sensors with chiroptical techniques is a straightforward approach to the stereochemical analysis of chiral molecules, especially in terms of process immediacy and labor. Stereodynamic probes typically consist of racemic mixtures of rapidly interconverting enantiomeric conformers able to recognize a chiral analyte and greatly amplify its chiroptical readout. A great number of sensors have been developed, but their activity is generally restricted to one or a few classes of chemicals, and the analysis outcome relies on precise knowledge of the probe and analyte concentrations. This aspect in particular limits the potential practical applications. Here we report an oxo-vanadium(V) aminotriphenolate complex that was found to act as a concentration-independent stereodynamic sensor for a wide range of compounds. The bare complex is CD-silent, but coordination of an enantioenriched substrate immediately gives rise to intense Cotton effects in the visible region. Furthermore, a geometry change during the substrate-complex interaction leads to a marked optical response, as witnessed by a strong red-shift of the probe absorption bands, thus allowing the generation of dichroic signals in an "interference-free" area of the spectrum. This peculiarity allows for a linear correlation at high wavelengths between the ee of the analyte and anisotropy g-factor. This parameter derives from the differential circularly polarized light absorption of the sample but is independent of concentration. The newly developed sensor based on a simple coordination process has an unprecedented general character in terms of substrate scope and employment.

Resonance Raman spectroscopy as an in situ probe for monitoring catalytic events in a Ru-porphyrin mediated amination reaction.

Resonance Raman microspectroscopy has been widely used to study the structure and dynamics of porphyrins and metal complexes containing the porphyrin ligand. Here, we have demonstrated that the same technique can be adapted to examine the mechanism of a homogeneously-catalysed reaction mediated by a transition-metal-porphyrin complex. Previously it has been challenging to study this type of reaction using in situ spectroscopic monitoring due to the low stability of the reaction intermediates and elevated-temperature conditions. We have made a straightforward modification to the sample stage on a microscope for time-lapsed Raman microspectroscopy from reaction mixtures in these media. The allylic amination of unsaturated hydrocarbons by aryl azides, which can be catalysed by a ruthenium-porphyrin complex, has been used as an illustrative example of the methodology. The mechanism of this particular reaction has been studied previously using density-functional theory and kinetic approaches. The Raman measurements support the mechanism proposed in the earlier publications by providing the first experimental verification of a precursor reaction complex between the aryl azide and the ruthenium metal ion, and evidence for the formation of a mono-imido intermediate complex under conditions of high concentration of the reactant olefin.

Correction: Resonance Raman spectroscopy as an in situ probe for monitoring catalytic events in a Ru-porphyrin mediated amination reaction.

Correction for 'Resonance Raman spectroscopy as an in situ probe for monitoring catalytic events in a Ru-porphyrin mediated amination reaction' by Paolo Zardi et al., Analyst, 2016, 141, 3050-3058.

Correction: Functionalized graphene-based materials for cementitious applications.

[This corrects the article DOI: 10.1039/D3RA06886B.].

Functionalized graphene-based materials for cementitious applications.

Graphene-based materials (GBM) are promising cementitious composite additives that can significantly improve the mechanical characteristics and durability of concrete due to their unique properties, such as high surface area and aspect ratio and excellent tensile strength, to name a few. To display their full potential, GBM have to be homogeneously dispersed into the aqueous environment of cement-based matrices. The present study addresses the issue of limited dispersibility in the aqueous media of GBM through the chemical functionalization of mono- and few-layer graphene structures with hydrophilic aryl sulfonate groups and shows that a series of mortar samples containing modified GBM exhibit increased flexural and compressive strength by up to 17% and 30%, respectively, compared to mortar references without additives.

Long-term durability of discarded cork-based composites obtained by geopolymerization.

Geopolymers are amorphous aluminosilicate inorganic polymers synthesized by alkaline activation characterized by a lower carbon footprint, greater durability, and excellent mechanical properties compared to traditional concrete, making them promising building materials for sustainable construction. To develop sustainable lightweight geopolymer-based building materials useful as fire resistant thermal insulation materials, we added 5 and 10 wt% of discarded cork dust, a readily available industrial by-product, to metakaolin before and after the alkaline activation with sodium hydroxide 8 M and sodium silicate solutions. We followed the chemical, microstructural, antibacterial, and physical properties of the resulting composites for up to 90 days in order to monitor their long-term durability. The presence of cork does not interfere with the geopolymerization process and in fact reduces the density of the composites to values around 2.5 g/cm3, especially when added after alkaline activation. The composites resulted in chemically stable matrices (less than 10 ppm of cations release) and filler (no hazardous compounds released) with a bacterial viability of around 80%. This study provides valuable insights into the tailoring of discarded cork-based composites obtained by geopolymerization with a porosity between 32 and 48% and a mechanical resistance to compression from 15 to 5 MPa, respectively, suggesting their potential as durable interior panels with low environmental impact and desirable performance.

Organic azides: "energetic reagents" for the intermolecular amination of C-H bonds.

This feature article provides an overview of the application of organic azides for the intermolecular amination of sp(3) and sp(2) C-H bonds. The catalytic activity of several metal complexes was reviewed underlining both synthetic and mechanistic aspects of the C-H amination. The majority of the aminated compounds reported in literature have been collected in this paper to provide a compendium of published procedures. In addition, the discussion of involved mechanisms has been included to assist the reader to envisage the future potential of organic azides in the synthesis of aza-derivatives.