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Excited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short‐lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long‐lived excited state, was identified as the competent species for the reduction of challenging organic substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox<−3 V vs. SCE in their excited states, determined by DFT and time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation of electron‐rich aryl chlorides and to form C−C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation. [ABSTRACT FROM AUTHOR]

We disclose the features of a category of reversible nucleophilic aromatic substitutions in view of their significance and generality in dynamic aromatic chemistry. Exchange of sulfur components surrounding arenes and heteroarenes may occur at 25 °C, in a process that one may call a "sulfur dance". These SNAr systems present their own features, apart from common reversible reactions utilized in dynamic covalent chemistry (DCC). By varying conditions, covalent dynamics may operate to provide libraries of thiaarenes with some selectivity, or conversion of a hexa(thio)benzene asterisk into another one. The reversible nature of SNAr is confirmed by three methods: a convergence of the products distribution in reversible SNAr systems, a related product redistribution between two per(thio)benzenes by using a thiolate promoter, and from kinetic/thermodynamic data. A four‐component dynamic covalent system further illustrates the thermodynamically‐driven formation of a thiacalix[2]arene[2]pyrimidine by sulfur component exchanges. This work stimulates the implementation of reversible SNAr in aromatic chemistry and in DCC. [ABSTRACT FROM AUTHOR]

Room temperature phosphorescence rarely occurs from pure organic molecules, especially in the solid‐state. A strategy for the design of highly emissive organic phosphors is still hard to predict, thus impeding the development of new functional materials with the desired optical properties. Herein, we analyze a family of alkyl and aryl‐substituted persulfurated benzenes, the latter representing a class of organic solid‐state triplet emitters able to show very high emission quantum yield at room temperature. In this work, we correlate structural parameters with the photophysical properties observed in different experimental conditions (diluted solution, crystalline and amorphous phase at RT and low temperature). Our results, corroborated by a detailed computational analysis, indicate a close relationship between the luminescence properties and i) the nature of the substituents on the persulfurated core, ii) the adopted conformations in the solid state, both in crystalline and amorphous phases. These factors contribute to characterize the lowest‐energy lying excited‐state, its deactivation pathways, the phosphorescence lifetime and quantum yield. These findings provide a useful roadmap for the development of highly performing purely organic solid‐state emitters based on the persulfurated benzene platform. [ABSTRACT FROM AUTHOR]

Copper indium sulfide quantum dots (CIS QDs) possess the desired optical properties to act as photoanodic material in photoelectrochemical cells, like a high molar absorption coefficient over the entire visible spectrum and long exciton lifetimes. The already reported procedures that utilize photoanodes based on such nanoparticles, however, exploit harsh conditions or utilize non‐scalable, expensive, and low‐yield syntheses. Here, the construction of CIS QDs adsorbed onto TiO2/FTO photoanodes (FTO = fluorine‐doped tin oxide) with a process aimed at avoiding these issues is proposed. In particular, the employment of dihydrolipoic acid as the ligand allows an easy and cost‐effective functionalization. CdS layers are deposited onto the nanoparticles to enhance the photoelectrochemical properties. Full characterization of the steady–state and transient photoelectrochemical properties of the electrodes is performed to gain information on the interfacial dynamics among the different components of the electrode. Maximum IPCEs of the order of 50% and a spectral sensitization extended up to 700 nm are obtained in the optimized conditions. [ABSTRACT FROM AUTHOR]

Dual photoredox catalysis is modifying the approach to sustainable metal catalysis based on metals in low oxidation state, as the use of stoichiometric metal as reductants are avoided. In this study, we showcase the potential use of vanadium in a dual photoredox process, allowing us to effectively control the formation of V(II) and its corresponding chemical reactions. A diastereoselective pinacol coupling with aromatic aldehydes is described. The process shows broad scope, and interestingly, unprotected salicylic aldehydes are compatible with the reaction protocol. Additionally, among all the ligands investigated we found that inexpensive bipyridines control the diastereoselection of the reaction favoring the d,l chiral compound (dr>20:1 for most of the aldehydes investigated). To promote the reaction and avoid an unproductive and not stereoselective radical coupling of the generated ketyl radical, the use of [DMQA]+, a stable organic dye, was found crucial. Furthermore, this dye possesses the remarkable capability of efficiently capturing light in the red segment of the visible spectrum, effectively raising efficiency of the protocol. The utilization of red light carries notable advantages in terms of penetration and safety, making it particularly significant. Moreover, careful photophysical investigations were able to give indications about the mechanism of the reaction. [ABSTRACT FROM AUTHOR]

The tetrahedral shape‐persistent molecule 14+, containing four identical pyridyl pyridinium units connected via a sp3 hybridized carbon atom, has been investigated in detail by means of steady‐state and time resolved spectroscopy. Remarkable photophysical properties are observed, particularly in comparison with protonated and methylated analogues (1H48+, 1Me48+), which exhibit substantially shorter excited state lifetimes and lower emission quantum yields. Theoretical studies have rationalized the behavior of the tetrameric molecules relative to the monomers, with DFT and TD‐DFT calculations corroborating steady‐state (absorption and emission) and transient absorption spectra. The behavior of the monomeric compounds (each consisting in one of the four identical subunits of the tetramers, i. e. 2+, 2H2+ and 2Me2+) considerably differs from that of the tetramers, indicating a strong electronic interaction between the subunits in the tetrameric species, likely promoted by the homoconjugation through the connecting sp3 C atom. 2+ is characterized by a peculiar S1‐S2 excited state inversion, whereas the short‐lived emitting S1 state of 2H2+ and 2Me2+ exhibits a partial charge‐transfer character, as substantiated by spectro‐electrochemical studies. Among the six investigated systems, only 14+ is a sizeable luminophore (Φem=0.15), which is related to the peculiar features of its singlet state. [ABSTRACT FROM AUTHOR]

For the first time, a dual photoredox‐ and titanocene‐catalyzed methodology for the regioselective access to α‐vinyl‐β‐hydroxy esters towards aldehyde allylation with 4‐bromobut‐2‐enoate is reported. The protocol is based on the Barbier‐type properties of the inexpensive and available Cp2TiCl2 in catalytic amount (5 mol%). The developed mild reaction conditions gave access to a library of differently functionalized α‐vinyl‐β‐hydroxy esters in moderate diastereoselectivity, employing the commercially available ethyl 4‐bromobut‐2‐enoate and both aromatic and aliphatic aldehydes. The reaction was realized under visible light irradiation, in the presence of an organophotocatalyst (3DPAFIPN, 2 mol%) combined with Hantzsch's ester as the sacrificial reductant. In contrast to other Barbier‐type reactions employing ethyl 4‐bromobut‐2‐enoate, the photoredox system ensures a better regioselectivity. Moreover, the use of preformed organometallic nucleophilic species (e. g. dienolborinates), and the need of metal reductants or stoichiometric amount of transition metals in low oxidation state for Barbier‐type reactions, is avoided. To support the experimental evidence, a detailed photophysical study shed light on the mechanism of the reaction. [ABSTRACT FROM AUTHOR]

To assess the value and reactivity of new photocatalysts (PCs), their performance should be evaluated in one or more established reactions and benchmarked against the performance using known PCs. Here, we evaluated our recently developed PC, pDTCz‐DPmS, in a C(sp)‐C(sp3) cross‐coupling reaction that had been documented in the literature. Previous findings indicated this reaction could not proceed in the absence of PC; however, under our conditions this was not the case. Without PC, a moderate product yield was obtained, while this yield increased significantly upon addition of pDTCz‐DPmS. UV‐Vis absorption studies indicated that the Hantzsch ester (HE) additive was acting as a competitive absorber of the light from the excitation source, and quenching studies confirmed that the HE was quenched by the radical precursor, N‐(acyloxy)phthalimide. Mechanistic investigations established that two parallel photosensitization pathways were in operation; a reductive quenching photocatalytic pathway (using pDTCz‐DPmS) and a sacrificial photoreductant pathway (employing HE). These pathways work synergistically to enhance the yield of target product. [ABSTRACT FROM AUTHOR]

The synthesis, structural, spectroscopic characterization, and DFT/TD‐DFT calculations of antimony corroles are reported herein. The studied complexes can be described as [(Corr)SbIII] and [(Corr)(oxo)SbV]2, where Corr is the trianion of corrole. All these complexes are diamagnetic in nature as is evident from sharp peaks with normal chemical shifts in the 1H NMR spectra. Single crystal XRD analysis reveals that the antimony(V) corrole complex is the bis‐μ‐oxo‐bridged dinuclear antimony(V). Both the tetra and hexa‐coordinated [(Corr)SbIII] and [(Corr)(oxo)SbV]2 antimony complexes adopt domed‐structure with weak d‐π electron coupling. The Sb−O bond distances in the co‐facial dimer of [(Corr)(oxo)SbV]2 are 1.9802(16) Å (DFT: 2.0141 Å) (for Sb1−O1), and 1.9639(17) Å (DFT: 1.9957 Å) (for Sb2−O2) respectively. We observed that even though iodosobenzene is frequently used to oxidize [(Corr)SbIII] species, the oxidation of [(Corr)SbIII] is indeed very facile in nature and it even occurred in the air‐equilibrated CHCl3 solution while storing for few days. Excitation of these antimony (III/V) corrole complexes in DCM/MeOH (1 : 1) at 77 K results in red emission with maxima at 640–720 nm. The singlet oxygen production of [(Corr)(oxo)SbV]2 has a quantum yield of 69 % and is two times higher than the analogous [(Corr)SbIII] derivatives. [ABSTRACT FROM AUTHOR]

The solar‐driven oxidation of biomass to valuable chemicals is rising as a promising anodic reaction in photoelectrochemical cells, replacing the sluggish oxygen evolution reaction and improving the added value of the energy conversion process. Herein, the photooxidation of 5‐hydroxymethylfurfural into furan dicarboxylic acid (FDCA) is performed in basic aqueous environment (borate buffer, pH 9.2), with the addition of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) as redox mediator. Because of its good stability, cost‐effectiveness, and nontoxicity, titanium‐modified hematite (Ti:Fe2O3) photoanodes are investigated to this aim, and their performance is tuned by engineering the semiconductor surface with a thin layer of Co‐based cocatalysts, i.e., cobalt iron oxide (CoFeOx) and cobalt phosphate (CoPi). Interestingly, the electrode modified with CoPi shows improved efficiency and selectivity toward the final product FDCA The source of this enhancement is correlated to the effect of the cocatalyst on the charge carrier dynamics, which is investigated by electrochemical impedance spectroscopy and intensity‐modulated photocurrent spectroscopy analysis. In addition, the results of the latter are interpreted through a novel approach called Lasso distribution of relaxation time, revealing that CoPi cocatalyst is effective in the suppression of the recombination processes and in the enhancement of direct hole transfer to TEMPO. [ABSTRACT FROM AUTHOR]

Photocrosslinking of polymers for industrial applications show undoubted advantages related to the mild conditions needed and the economical equipment. However, some issues include: the use of (i) mercury lamps as light sources, which poses concerns about safety and energy consumption, (ii) typical additives, such as halogen‐free flame‐retardant fillers (HFFR) are powdered materials, which can scatter UV photons and avoid a deep penetration of the light. In this study, we explore the UV‐curing of an innovative EVA‐POE blend containing hydrotalcite and aluminum hydroxide as HFFR in the presence of a 370‐nm UV LED, namely Ekopren® XI1321, a plastic used as coverage for electric cables. Two commercially available photoinitiators (benzophenone and ethyl Michler's ketone) were analyzed as well as two crosslinking coagents widely used in industry, that is, triallyl cyanurate and trimethylolpropane trimethacrylate. A comparison with pure EVA and LDPE was performed to show a higher cross‐linked content of the proposed blend, even in the presence of light scattering mineral fillers at high concentration. [ABSTRACT FROM AUTHOR]

A new meso‐naphthalenyl BODIPY was designed for the efficient generation of long‐lived triplet excited state under irradiation with green light. The new, heavy atom‐free organic chromophore was employed in a benchmark example of dual palladium and photoredox catalysis, highlighting the applications of BODIPY dyes as photoredox catalysts. [ABSTRACT FROM AUTHOR]

A regioselective vinylation of aromatic and aliphatic aldehydes promoted by the merging of photoredox and nickel catalysis is here reported. A comprehensive investigation on the reaction conditions allowed the disclosure of a valid and reproducible protocol based on a nickel‐mediated reductive coupling approach under visible light irradiation. The employment of 3CzClIPN (2,4,6‐tris(carbazol‐9‐yl)‐5‐chloro‐isophthalonitrile) as the photocatalyst and Hantzsch's ester as the sacrificial organic reductant replace the use of boron‐, silicon‐ or zinc‐based reducing agents, making this method a worthy alternative to the already known protocols. The developed mild reaction conditions allow the access to a wide range of substituents decorating both the aldehyde and the alkyne. Moreover, careful photophysical investigations shed light on the mechanism of the reaction. [ABSTRACT FROM AUTHOR]

The article titled "The Sulfur Dance" Around Arenes and Heteroarenes - the Reversible Nature of Nucleophilic Aromatic Substitutions explores the reversible nature of nucleophilic aromatic substitutions in dynamic aromatic chemistry. The front cover of the journal features a depiction of a circle dance with musical notes around a sulfurated benzene ring, symbolizing the exchanges of sulfur components surrounding arenes and heteroarenes. The research article, authored by J.-L. Schmitt, J.-M. Lehn, M. Gingras, and their colleagues, provides more detailed information on this topic. [Extracted from the article]

The synthesis of regioisomeric asterisks (5) and (6) incorporating a benzene core with six 1‐naphthylthio or six 2‐naphthylthio arms are reported in search for new materials with optoelectronic properties. The consequences on the extension of a π system surrounding a persulfurated benzene core provide a new avenue to study the structural, photophysical, and chemical properties of such family of all‐organic phosphors. It also diverts the persulfuration mechanism after two radical cyclizations for making a [5]dithiohelicene by‐product (7) and favors dynamic sulfur component exchange reactions surrounding the core. These exchanges convert asterisks (5) and (6), non‐phosphorescent at 20 °C to the highly phosphorescent (4) (ϕ ∼100 %, solid state at 20 °C). For asterisks (5) and (6), the absence of the typical phosphorescence of the per(phenylthio)benzene core in the solid state at 20 °C and the presence of a weak naphthalene‐based phosphorescence at 77 K is attributed to an energy transfer from the triplet state of the persulfurated benzene core to the outer naphthalene moieties, resulting in an antenna system. [ABSTRACT FROM AUTHOR]

Organochromium(III) species are multipurpose nucleophiles used in the synthesis of complex organic molecules due to their high functional group tolerance and extraordinary chemoselectivity for aldehydes. The preparation of organochromium(III) species starting from organic halides requires the use of a stoichiometric amount of chromium(II) salts or a catalytic amount of chromium(III) salts in the presence of stoichiometric reductants (such as Mn(0)). Recently, radicals formation from readily available alkenes, followed by their trapping with stoichiometric or catalytic amount of chromium(II) salts were reported in photoredox conditions for the generation of Cr(III) organometallic species. In this paper we disclose a real Nozaki‐Hiyama reaction (NH) in which photoredox conditions enable the preparation of Cr(III) allyl reagents starting from available allyl halides and stable Cr(III) salts. [ABSTRACT FROM AUTHOR]

Tetraphenylmethane (TPM) and tetraphenylethylene (TPE) are among the most common rigid molecular architectures able to spatially arrange four peripheral functional groups. The aim of this Review is to provide a thorough description of the properties that supramolecular systems consisting of four chromophores (common supramolecular motifs, ligands, redox centers and conventional luminophores such as polypyridyl ligands, viologens, and azobenzene units) attached to TPM and TPE cores can show. Specifically, the photophysical properties of these molecules as well as the electronic interactions of the chromophores either in the ground or in the excited states will be highlighted and discussed, outlining the relationship among cores and outer subunits. [ABSTRACT FROM AUTHOR]

Here we report a practical, highly enantioselective photoredox allylation of aldehydes mediated by chiral nickel complexes with commercially available allyl acetate as the allylating agent. The methodology allows the clean stereoselective allylation of aldehydes in good to excellent yields and up to 93 % e.e. using a catalytic amount of NiCl2(glyme) in the presence of the chiral aminoindanol‐derived bis(oxazoline) as the chiral ligand. The photoredox system is constituted by the organic dye 3DPAFIPN and a Hantzsch's ester as the sacrificial reductant. The reaction proceeds under visible‐light irradiation (blue LEDs, 456 nm) at 8–12 °C. Compared to other published procedures, no metal reductants (such as Zn or Mn), additives (e.g. CuI) or air‐sensitive Ni(COD)2 are necessary for this reaction. Accurate DFT calculations and photophysical experiments have clarified the mechanistic picture of this stereoselective allylation reaction. [ABSTRACT FROM AUTHOR]

Tetraphenylmethane appended with four pyridylpyridinium units works as a scaffold to self‐assemble four ruthenium porphyrins in a tetrahedral shape‐persistent giant architecture. The resulting supramolecular structure has been characterised in the solid state by X‐ray single crystal analysis and in solution by various techniques. Multinuclear NMR spectroscopy confirms the 1 : 4 stoichiometry with the formation of a highly symmetric structure. The self‐assembly process can be monitored by changes of the redox potentials, as well as by modifications in the visible absorption spectrum of the ruthenium porphyrin and by a complete quenching of both the bright fluorescence of the tetracationic scaffold and the weak phosphorescence of the ruthenium porphyrin. An ultrafast photoinduced electron transfer is responsible for this quenching process. The lifetime of the resulting charge separated state (800 ps) is about four times longer in the giant supramolecular structure compared to the model 1 : 1 complex formed by the ruthenium porphyrin and a single pyridylpyridinium unit. Electron delocalization over the tetrameric pyridinium structure is likely to be responsible for this effect. [ABSTRACT FROM AUTHOR]

A new platinum(II) porphyrin complex has been synthesized and characterized via various spectroscopic techniques. Single‐crystal XRD analysis reveals that the geometry around the Pt(II) center is near the perfect square planar geometry. The Pt(II)−N bond distances are in the ranges of 2.005 Å–2.020 Å. The platinum(II) porphyrin derivative exhibited one reversible oxidative couple at +1.10 V and a reversible reductive couple at −1.47 V versus Ag/AgCl. In deaerated dichloromethane solution at 298 K, a strong phosphorescence is observed at 660 nm, with emission quantum yield of 35 % and lifetime of 75 μs. Upon excitation of the acenaphthene chromophores at 300 nm, sensitised phosphorescence of the Pt(II) porphyrin is observed with a unitary efficient energy transfer, demonstrating that this system behaves as a light harvesting antenna. The red phosphorescence is strongly quenched by oxygen, resulting in singlet oxygen production with a very high quantum yield of 88 %. This result indicates that this Pt(II) porphyrin is an excellent photosensitizer for the production of singlet oxygen and will have potential applications in the field of photodynamic therapy as well as oxygen sensors. [ABSTRACT FROM AUTHOR]

The preparation of homoallylic alcohols by addition of organometallic allyl compounds to carbonyls is an important strategy in organic chemistry. Allylating organometallic cobalt species can be generated employing stoichiometric quantities of Zn acting as reductant. To avoid the employment of stoichiometric amount of Zn, we have developed an allylation reaction of aromatic and aliphatic aldehydes promoted by photoredox catalysis in the presence of a cobalt complex, and we present herein a full account of our research. In the presence of the abundant CoBr2 (10 mol %), 4,4′‐di‐tert‐butyl‐2,2′‐dipyridyl (dtbbpy, 10 mol %), allyl acetate (3 equiv.), [Ir(dtbbpy)(ppy)2]PF6 (ppy=2‐phenylpyridine, 2 mol %), and N,N‐diisopropylethylamine (4 equiv.), an allylation of aldehydes is taking place, in moderate to good yields. Substrates scope, limitations, and photophysical investigations of this new process are reported. [ABSTRACT FROM AUTHOR]

High level time‐dependent density functional theory (TD‐DFT) computational modeling of coumarin dyes has been exploited for guiding the design of effective photocatalysts (PCs). A library of coumarins were investigated from the theoretical point of view and photophysical/electrochemical properties (absorption and emission spectra, E00, oxidation and reduction potentials) were evaluated. Comparison with literature values reported for a few candidates has been used for assessing the level of theory. On the basis of the results obtained, new strongly reducing PCs [Eox(PC.+/PC*)=−2.1 – −2.0 V vs SCE] were discovered. Through the computational study of structure‐properties relationships, a number of coumarins derivatives have been synthesized and evaluated in the pinacol coupling of aldehydes as the model reaction. The new organic photoredox catalysts show experimental photophysical and electrochemical data in accordance with the ones predicted by calculation, with excited state reduction potentials surpassing those of highly reducing transition metal‐based PCs. A careful investigation of their behavior as PC has revealed crucial issues that need to be taken into consideration in the general photoredox catalysis, shedding light on the use of these PC in the pinacol, as well as, in other photoredox reactions. [ABSTRACT FROM AUTHOR]

Pyrene-based materials have gained considerable attention as stimuli-responsive chemical sensors. We designed a polysulfurated arene system based on a tetra(phenylthio)pyrene core decorated with four carboxylic acid units. Three different regioisomers, ortho, meta and para were studied in organic and aqueous solution. These systems are soluble in water at pH-8 due to the deprotonation of carboxylic acids. The addition of metal ions cannot only quench the fluorescence of the central pyrene core, but also control the formation of three-dimensional nanoscopic objects in a dual mode function. Several divalent metal ions were tested and compared. Addition of ethylenediaminetetraacetic acid (EDTA) disassembles the nonemissive supramolecular system and restores the initial fluorescence of the pyrene core. [ABSTRACT FROM AUTHOR]

Metallosalen are privileged complexes that have found important applications in catalysis. In addition, their luminescent properties have also been studied and used for sensing and biological applications. Salen metal complexes can be efficient photosensitizers, but they can also participate to electron transfer processes. Indeed, we have found that commercially available [Al(Salen)Cl] is an efficient photoredox catalyst for the synergistic stereoselective reaction of alkyl aldehydes with different bromo ketones and malonates to give the corresponding enantioenriched α‐alkylated derivatives. The reaction was performed in the presence of a MacMillan catalyst. [Al(Salen)Cl] is able to replace ruthenium complexes, showing that also aluminum complexes can be used in promoting photoredox catalytic reactions. [ABSTRACT FROM AUTHOR]

Abstract: The herein reported visible‐light‐activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63–99 % yields and with excellent enantioselectivities of up to >99 % ee. The reactions are catalyzed by a single bis‐cyclometalated chiral‐at‐metal rhodium complex (2–8 mol %) which after coordination to the cyclopropane generates the visible‐light‐absorbing complex, lowers the reduction potential of the cyclopropane, and provides the asymmetric induction and overall stereocontrol. Enabled by a mild single‐electron‐transfer reduction of directly photoexcited catalyst/substrate complexes, the presented transformations expand the scope of catalytic asymmetric photocycloadditions to simple mono‐acceptor‐substituted cyclopropanes affording previously inaccessible chiral cyclopentane and cyclopentene derivatives. [ABSTRACT FROM AUTHOR]

A shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound. Furthermore, there is an increase of the apparent pimerization constant by increasing the concentration of reduced bipyridinium units. These results have been interpreted by the fact that pimerization is favored in the tetrahedrally shaped molecule because of a cooperative mechanism. Each multiply reduced molecule can indeed undergo multiple intermolecular interactions that enhance the stabilization of the system, also leading to hierarchical supramolecular growth. The resulting supramolecular system formed by such intermolecular pimerization should exhibit a diamond-like structure, as suggested by a simplified modeling approach. The intermolecular nature of the pimerization process occurring in the tetramer has been demonstrated by measuring the corresponding bimolecular rate constant by pulsed radiolysis experiments. [ABSTRACT FROM AUTHOR]

Cover Feature: Synthesis, Characterization, and Singlet Oxygen Sensitization by Antimony (III/V) Corrole Complexes (Eur. J. Inorg. The quantum yield of singlet oxygen production for the antimony(V) dimer has a value of 69 % and is two times higher compared to that of antimony(III) corroles. Keywords: Antimony; Corroles; Density functional calculations; Photochemistry; Singlet oxygen EN Antimony Corroles Density functional calculations Photochemistry Singlet oxygen 1 1 1 08/25/23 20230823 NES 230823 B The Cover Feature b shows a bis- I i -oxo-bridged dinuclear antimony(V) complex. [Extracted from the article]

The synthesis of O-doped polyaromatic hydro- carbons in which two polycyclic aromatic hydrocarbon sub units are bridged through one or two O atoms has been achieved. This includes high-yield ring-closure key steps that, depending on the reaction conditions, result in the formation of furanyl or pyranopyranyl linkages through intramolecular C−O bond formation. Comprehensive photophysical measurements in solution showed that these compounds have exceptionally high emission yields and tunable absorption properties throughout the UV/Vis spectral region. Electrochemical investigations showed that in all cases O annulation increases the electron-donor capabilities by raising the HOMO energy level, whereas the LUMO energy level is less affected. Moreover, third-order nonlinear optical (NLO) measurements on solutions or thin films containing the dyes showed very good values of the second hyperpolarizability. Importantly, poly(methyl methacrylate) films containing the pyranopyranyl derivatives exhibited weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, and thus revealed them to be exceptional organic materials for photonic devices. [ABSTRACT FROM AUTHOR]

The bis(dansylated) polyoxometalate ( nBu4N)4[γ-SiW10O36{(Me2N)C10H6SO2NH(CH2)3Si}2O] has been investigated to establish the impact of the inorganic polyanionic domain on the photophysical behaviour of the appended dansyl chromophore. The interactions of this molecular hybrid with Lewis acids (lanthanide cations) and with an aromatic cationic molecule ( N, N′-2,7-didecyldiazapyrenium) have also been monitored by multiple techniques, including spectrofluorimetry, Z-potential, 1H NMR spectroscopy, transmission electron microscopy. The different spectral behaviour, coupled with the morphological evolution of the resulting nanostructures, highlights the capability of the hybrid polyoxometalate to interact, acting as a ditopic receptor, with different chemical substrates. [ABSTRACT FROM AUTHOR]

Photocatalysis enables the cascade reactions of indoles and CBr4 in MeOH through a C(sp2)H functionalization/methanolysis sequence. The title reaction provides an efficient access to indole 2- and 3-carboxylates in a single operation (no preinstallation of protecting as well as directing groups was required) with good yields under mild reaction conditions. [ABSTRACT FROM AUTHOR]

An essay is presented on light and its role in the conversation of solar energy into electrical power. It highlights its energy aspects as well as interaction with matter. An overview of its redox reaction and interconversion with chemical energy as well as semiconductor-based photocatalytic systems (PCs) and photoelectrochemical cells (PECs) is also presented.

Graphene-metal composites have potential as novel catalysts due to their unique electrical properties. Here, we report the synthesis of a composite material comprised of monodispersed platinum nanoparticles on high-quality graphene obtained by using two different exfoliation techniques. The material, prepared via an easy, low-cost and reproducible procedure, was evaluated as an electrocatalyst for the hydrogen evolution reaction. The turnover frequency at zero overpotential (TOF0 in 0.1 m phosphate buffer, pH 6.8) was determined to be approximately 4600 h−1. This remarkably high value is likely due to the optimal dispersion of the platinum nanoparticles on the graphene substrate, which enables the material to be loaded with only very small amounts of the noble metal (i.e., Pt) despite the very highly active surface. This study provides a new outlook on the design of novel materials for the development of robust and scalable water-splitting devices. [ABSTRACT FROM AUTHOR]

A tetrahedral shape-persistent molecule equipped with four terpyridine ligands can form an oligomeric structure upon complexation with metal ions, in which two terpyridine units are intermolecularly connected via a metal ion. The most interesting results were obtained upon binding of lanthanide ions, whose luminescence is sensitized by the ligand. In particular, dual luminescent probes were obtained upon concomitant complexation of two different lanthanide ions, such as EuIII and NdIII. [ABSTRACT FROM AUTHOR]