High-valent actinyl (AnO; An = U, Np and Pu) complexation with TEtraQuinoline (TEQ) ligand - a DFT study.

A recently synthesised novel macrocycle composed of four quinoline units called TEtraquinoline (TEQ) (, 2023, (4), 2609-2618) was reported to exhibit transition metal complexation ability. Meanwhile, there is a growing interest in different binding motifs for radioactive and toxic actinides. In this study, we modelled high-valent actinyl (AnO), An = U, Np, Pu; = 1, 2, 3 complexes of TEQ and studied their geometric and electronic properties using scalar relativistic density functional theory (SR-DFT).

Design of Isoindigo-Based Small-Molecule Donors for Bulk Heterojunction Organic Solar Cell Applications in Combination with Nonfullerene Acceptors.

The development of small-molecule organic solar cells with the required efficiency depends on the information obtained from molecular-level studies. In this context, 39 small-molecule donors featuring isoindigo as an acceptor moiety have been meticulously crafted for potential applications in bulk heterojunction organic solar cells. These molecules follow the D-A-D-A-D and D-A-π-D-π-A-D framework.

Starch Gel Electrolyte and its Interaction with Trivalent Aluminum for Aqueous Aluminum-Ion Batteries: Enhanced Low Temperature Electrochemical Performance.

This study explores trivalent Al interaction with aqueous starch gel in the presence of two different anions through salting effect. Salting-out nature of Al(SO)·18HO with starch gel causes precipitation of starch; this happens due to competitive anion-water complex formation over starch-water interaction, thereby reducing polymer solubility. Salting-in effect of AlCl with starch gel happens through Al cation interaction with hydroxyl group of starch and increases polymer solubility, making gel electrolyte viable for battery applications.

Elucidation of the extraction of trivalent actinides using the DOHyA-HDEHP system: an experimental and theoretical approach.

A combined solvent system composed of an acidic and a neutral extractant is demonstrated as an effective system for the mutual separation of lanthanides and actinides from nitric acid solutions. The geometry and stability of various possible complexes formed under extraction and stripping conditions in a combined solvent system composed of ,-dioctyl hydroxyacetamide (DOHyA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) in the -dodecane medium were studied both experimentally and theoretically. Experimental observations of the distribution ratios of Am(III) and Eu(III) in the combined solvent system revealed synergistic extraction of trivalent metal ions at all nitric acid concentrations.

Computational study of core modified dipyriamethyrin for the competitive complexation of Am/Cm from their trichlorides.

In the process of handling and storage of radioactive actinides it is essential to selectively sequester the minor actinides, such as Am and Cm, through a competitive complexation process. Herein we computationally designed two core modified ligands (L2 and L3) through systematic oxygen substitution at the NH sites of dipyriamethyrin (L1_2H), a hexadentate expanded porphyrin, and studied their competitive complexation towards trivalent actinides (An = Am/Cm) from their trichlorides using density functional theory (DFT). We observed shorter An-N bonds and longer An-O bonds in complexes based on core modified ligands (L2 and L3).

Tuning the CO Reduction Selectivity of an Immobilized Molecular Ag Complex beyond CO.

The electrochemical reduction of carbon dioxide (CO) to produce fuels and chemicals has garnered significant attention. However, achieving control over the selectivity of the resulting products remains a challenging task, particularly within molecular systems. In this study, we employed a molecular silver complex immobilized on graphitized mesoporous carbon (GMC) as a catalyst for converting CO into CO, achieving an impressive selectivity of over 90% at -1.

Polarity-Induced Morphological Transformation with Tunable Optical Output of Terpyridine-Phenanthro[9,10-]imidazole-Based Ligand and Its Zn(II) Complexes with - Characteristics.

Self-assembled nanostructures obtained from various functional π-conjugated organic molecules have been able to draw substantial interest due to their inherent optical properties, which are imperative for developing optoelectronic devices, multiple-color-emitting devices with color-tunable displays, and optical sensors. These π-conjugated molecules have proven their potential employment in various organic electronic applications. Therefore, the stimuli-responsive fabrication of these π-conjugated systems into a well-ordered assembly is extremely crucial to tuning their inherent optical properties for improved performance in organic electronic applications.

Periodic Trends in the Stabilization of Actinyls in Their Higher Oxidation States Using Pyrrophen Ligands.

Owing to the prominent existence and unique chemistry of actinyls, their complexation with suitable ligands is of significant interest. The complexation of high-valent actinyl moieties (An = U, Np, Pu and Am) with the acyclic sal-porphyrin analogue called "pyrrophen" (L) and its dimethyl derivative (L) with four nitrogen and two oxygen donor atoms was studied using relativistic density functional theory. Based on the periodic trends, the [UO-L/L] complexes show shorter bond lengths and higher bond orders that increase across the series of pentavalent actinyl complexes mainly due to the localization of the 5f orbitals.

Understanding the Coordination Chemistry of Am/Cm in the DOTA Cavity: Insights from Energetics and Electronic Structure Theory.

The minor actinides Am/Cm show multiple possibilities for coordination, providing great opportunities for their extraction and adsorption separation. Herein, we report complexation in an aqueous medium of Am/Cm in the DOTA (HDOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) cavity with axial ligands (OH, F, and HO), based on the energetics and electronic structure properties using density functional theory (DFT). The formation and substitution reactions of OH-capped complexes are more likely to occur due to their enhanced hydration Gibbs free energies, followed by F, and then HO.

Iodo-sulphonylation of 1,6-enynones: a metal-free strategy to synthesize -substituted succinimides.

An iodine-mediated radical cyclization of 1,6-enynones with sulphonyl hydrazides using -butyl hydroperoxide (TBHP) as the oxidant has been developed for the synthesis of iodo-sulphonylated-succinimide derivatives. The notable advantages of the developed method are metal-free conditions, broad functional group tolerance, column chromatography-free purification, high stereoselectivity ( isomer), shorter reaction times, and the cascade construction of three new bonds (C-S, C-I, and C-C). The synthetic application of the iodo-functionality has been extended to the Heck coupling reaction with acrylonitrile and to the Suzuki coupling reaction with benzene boronic acid.

Why and not ? - Molecular dynamics and DFT study on selective separation of dihaloethene isomers using perethylated pillar[5]arene.

The separation of mixtures of isomers is a daunting task. It is found that perethylated pillar[5]arene can separate -dichloroethene from its isomer. This work deals with the host-guest interactions and the selective separation of dihaloethene over -dihaloethene using perethylated pillar[5]arene.

Chemical bonding in actinyl(V/VI) dipyriamethyrin complexes for the actinide series from americium to californium: a computational investigation.

The separation of minor actinides in their dioxocation (, actinyl) form in high-valence oxidation states requires efficient ligands for their complexation. In this work, we evaluate the complexation properties of actinyls including americyl, curyl, berkelyl, and californyl in their pentavalent and hexavalent oxidation states with the dipyriamethyrin ligand (L) using density functional theory calculations. The calculated bond parameters show shorter AnO bonds with covalent character and longer An-N bonds with ionic character.

Computational Characterization of Ac-DOTA Complexes in Aqueous Solution.

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complexes of Ac with HO, dimethyl sulfoxide (DMSO), OH, and F as axial ligands were studied using density functional theory. Formation of the [Ac(DOTA)(OH)] and [Ac(DOTA)(F)] complexes is predicted to be significantly more favorable than that of [Ac(DOTA)(HO)] and [Ac(DOTA)(DMSO)] because of the enhanced relative Gibbs free energies. Further electronic structure analyses demonstrate that the type and nature of the bond between Ac and the ligand donor atom is the main driving force that determines the thermodynamic stability of the complexes.

Computational Study of Actinyl Ion Complexation with Dipyriamethyrin Macrocyclic Ligands.

Relativistic density functional theory has been employed to characterize [AnO(L)] complexes, where An = U, Np, Pu, and Am, and L is the recently reported hexa-aza porphyrin analogue, termed dipyriamethyrin, which contains six nitrogen donor atoms (four pyrrolic and two pyridine rings). Shorter axial (An═O) and longer equatorial (An-N) bond lengths are observed when going from An to An. The actinide to pyrrole nitrogen bonds are shorter as compared to the bonds to the pyridine nitrogens; the former also play a dominant role in the formation of the actinyl (VI and V) complexes.

Diels-Alder reaction of tetraarylcyclopentadienones with benzo[b]thiophene S,S-dioxides: an unprecedented de-oxygenation vs. sulfur dioxide extrusion.

Diels-Alder reaction of tetraarylcyclopentadienones with benzo[b]thiophene dioxides in xylenes at reflux led to the formation of tetra aryl-substituted dibenzothiophene as well as penta aryl-substituted benzene analogues depending on the influence of aryl substituents present on cyclopentadienones. The intermediate dihydrodibenzothiophene-dioxides underwent aromatization either through de-oxygenation or extrusion of sulfur dioxide to furnish substituted dibenzothiophenes or benzenes.

Proton affinities of pertechnetate (TcO) and perrhenate (ReO).

The anions pertechnetate, TcO4-, and perrhenate, ReO4-, exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO4-)(H+)(ReO4-).

Aromaticity-Photovoltaic Property Relationship of Triphenylamine-Based D-π-A Dyes: Leads from DFT Calculations.

D-π-A-based dyes find a wide range of applications in molecular electronics and photovoltaics in general and dye-sensitized solar cells (DSSC) in particular. We speculated whether there exists a relationship between the degree of aromaticity of the π-spacers used in the D-π-A type dyes and their structural, electronic, energetic, photophysical, and intramolecular charge transfer properties. Triphenylamine (TPA) and cyanoacrylic acid (CAA) have been chosen as the donor and acceptor, respectively.

A solution processable fluorene-fluorenone oligomer with aggregation induced emission enhancement.

Herein, we report a novel solution processable fluorenone based small molecule with an Aggregation Induced Emission Enhancement (AIEE) property. In contrast to previous reports, the presence of the fluorenone moiety in FF triggers the AIEE property.