A Series of Iron(II)-NHC Sensitizers with Remarkable Power Conversion Efficiency in Photoelectrochemical Cells**

A series of six new Fe(II)NHC-carboxylic sensitizers with their ancillary ligand decorated with functions of varied electronic properties have been designed with the aim to increase the metal-to- surface charge separation and light harvesting in iron-based dye-sensitized solar cells (DSSCs). ARM130 scored the highest efficiency ever reported for an iron-sensitized solar cell (1.83 %) using Mg²⁺ and NBu₄I-based electrolyte and a thick 20 μm TiO₂ anode. Computational modelling, transient absorption spectroscopy and electrochemical impedance spectroscopy (EIS) revealed that the electronic properties induced by the dimethoxyphenyl-substituted NHC ligand of ARM130 led to the best combination of electron injection yield and spectral sensitivity breadth.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.     

SYNTHESIS AND THERMAL REARRANGEMENT OF 2-ALKOXYCARBONYL-3-ALKYL-4H-BENZO[b][1,4]THIAZINES

Abstract

The title compounds (4b-d) together with the benzothiazolines (5b-d) have been obtained by a reaction between 2,2′-dithiodianiline (1) and β-keto esters (2b-d). The reaction between 1 and the β-keto ester 2a gives 1,4-benzothiazine 3a in addition to the benzothiazoline 5a.

It has been established that the 1,4-benzothaizines 4b-d undergo an acid-catalysed thermal rearrangement involving a [1,3] shift of the sulfur atom, giving rise to the isomeric 1,4-benzothiazines 3b-d.     

Synthesis and characterisation of a silicon oxide film solid-phase extraction system for lead traces determination: an all the way green analytical method

In this work, an all the way green analytical procedure based on a silicon oxide film-solid phase extraction system is proposed for lead traces determination. From the synthesis of a solid phase extraction (SPE) system and throughout the metal preconcentration and determination only aqueous media were employed. Characterisation of the film was carried out by Scanning Electron Microscopy and Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy. Preconcentration conditions, prior to Pb(II) Electrothermal Atomic Absorption Spectrometry (ETAAS) determination, such as adsorption and desorption time, pH and temperature, were optimised. Langmuir, Freundlich and Dubinin-Radushkevich isotherm models were analysed along with the evaluation of adsorption energy and standard free energy (ΔG ⁰). The greatest adsorption was obtained with incubation at pH 7 and 37°C. By using a small volume of 0.5?mol?L^?1 HNO₃ (0.5?mL) lead was desorbed from the silicon oxide film after 2?h incubation, generating low amount of waste. The films showed better adjustment for the Langmuir model (R^{2 ?}=?0.989). The detection limit (3.29σ) for Pb(II) was 0.228?µg?L^?1. The developed procedure is 10-fold more sensitive in comparison to direct ETAAS determination. Recovery values from soft tap-water and soft well-water were above 95%. When hard water was analysed, Pb(II) adsorption was found to be interfered by Mg²⁺ and Ca²⁺. After five preconcentration cycles relative recovery was found not to decay below 90%, indicating that the silicon oxide film could be used for multiple lead determinations.     

Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H,Me, Ph)

The reactivity of a series of iridium? pyridylidene complexes with the formula [Tp^Me2Ir(C₆H₅)₂(C(CH)₃C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H₂, O₂, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e^? unsaturated [Tp^Me2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H₂ is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO₂, and H₂C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH₂CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH₂)N moiety. C₆H₅(C?O)H and C₆H₅C?CH react with formation of Ir? C₆H₅ and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O₂ is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.     

A Highly Luminescent Tetramer from a Weakly Emitting Monomer: Acid‐ and Redox‐Controlled Multiple Complexation by Cucurbit[7]uril

The tetrahedral, shape‐persistent molecule 1 ⁴⁺, containing four pyridylpyridinium units connected through a central carbon atom, exhibits unexpected photophysical properties including a substantially redshifted absorption (2350 cm^?1) and a very strong fluorescence (Φ_em=40 %), compared with the monomer 2 ⁺ (Φ_em=0.4 %). Density functional theory calculations on the structure and spectroscopic properties of 1 ⁴⁺ and 2 ⁺ show that exciton interactions, homoconjugation, and orbital nature account for the observed differences in their photophysical properties. The protonated tetramer binds four cucurbit[7]uril molecules and the host/guest interactions can be controlled by chemical (acid/base) as well as redox stimuli.     

Isolation and characterization of cellulose nanofibers from banana peels

Cellulose nanofibers were isolated from banana peel using a combination of chemical treatments, such as alkaline treatment, bleaching, and acid hydrolysis. The suspensions of chemically treated fibers were then passed through a high-pressure homogenizer 3, 5, and 7 times, to investigate the effect of the number of passages on the properties of the resulting cellulose nanofibers. The cellulose nanofibers isolated in this study had a dry basis yield of 5.1 %. Transmission electron microscopy showed that all treatments effectively isolated banana fibers in the nanometer scale. The micrographs of the process steps used to isolate the nanofibers revealed gradual removal of amorphous components. Increasing number of passages in the homogenizer shortened the cellulose nanofibers while furnishing more stable aqueous suspensions with zeta potential values ranging from ?16.1 to ?44.1 mV. All the samples presented aspect ratio in the range of long nanofibers, hence being potentially applicable as reinforcing agents in composites. X-ray diffraction studies revealed that homogenized nanofiber suspensions were more crystalline than non-homogenized suspensions. Fourier transform infrared spectroscopy confirmed that alkaline treatment and bleaching removed most of the hemicellulose and lignin components present in the banana fibers. Thermal analyses revealed that the developed nanofibers exhibit enhanced thermal properties. In general, the nanoparticles isolated from the banana peel have potential application as reinforcing elements in a variety of polymer composite systems.     

Adducts of 2-aminothiophenol with acetylenic nitriles or esters and their conversion into benzothiazoles and/or 1,4-benzothiazines

The reaction between 2-aminothiophenol 1 and acetylenic nitriles or esters 2a-d leads to the vinyl thio-ethers 3a-d. The conversion of 3 into benzothiazoles 8 and/or 1,4-benzothiazines 9 , in boiling dimethyl sulfoxide, has been achieved. A possible pathway involving benzothiazolines 5 as key intermediates is suggested.     

Vinyl acetate formation by the reaction of ethylene with acetate species on oxygen-covered Pd(111)

The reaction pathway of vinyl acetate synthesis is scrutinized by reacting gas-phase ethylene (at an effective pressure of 1 x 10-4 Torr) with eta2-acetate species (with a coverage of 0.31 +/- 0.02 monolayer) on a Pd(111)-O(2x2) model catalyst surface in ultrahigh vacuum. It is found that the 1414 cm-1 infrared feature due to the symmetric OCO stretching mode of the acetate species decreases in intensity due to reaction with gas-phase ethylene, while temperature-programmed desorption experiments demonstrate that vinyl acetate is formed. The formation of ethylidyne species is detected when almost all of the acetate species have been removed. The experimental removal kinetics are reproduced by a model in which adsorbed acetates react with an ethylene-derived (possibly ethylene or vinyl) species, where ethylene adsorption is blocked by the acetate present on the surface.