Radical and diradical states of bis(molybdenocene dithiolene) complexes.

The synthesis and characterization of two bis(dithiolene) proligands involving heteroatomic linkers such as 1,4-dithiine and dihydro-1,4-disiline between the two protected dithiolene moieties are described. Two bimetallic complexes involving these heteroatomic bridges between two redox active bis(cyclopentadienyl)molybdenum dithiolene moieties have been synthesized and characterized by electrochemistry, spectroelectrochemistry, and their properties rationalized with (TD-)DFT. Cyclic voltammetry experiments show sequential oxidation of the two redox centers with Δ values between successive one-electron transfers varying according to the nature of the bridge.

Ionic Conductivity and Structure of Glasses Synthesized by Mechanical-Milling Methods in the [NaS]-(100 - ) [0.5GeS-0.5GaS] System.

Chalcogenide glasses in the NaS-GeS-GaS pseudoternary system were synthesized using a combination route of melt-quenching and mechanical-milling methods. First, a glass rich in germanium (90GeS-10GaS) is synthesized by melt-quenching synthesis in a silica tube sealed under vacuum. This glass is used as a precursor for the second step of mechanochemistry to explore the NaS-GeS-GaS pseudoternary system.

Kinetic Delay in Cooperative Supramolecular Polymerization by Redefining the Trade-Off Relationship between H-Bonds and Van der Waals/π-π Stacking Interactions.

We here present how rebalancing the interplay between H-bonds and dispersive forces (Van der Waals/π-π stacking) may induce or not the generation of kinetic metastable states. In particular, we show that extending the aromatic content and favouring the interchain VdW interactions causes a delay into the cooperative supramolecular polymerization of a new family of toluene bis-amide derivatives by trapping the metastable inactive state.

A Bimetallic Benzene-1,2,4,5-Tetrathiolate (btt) Molybdenocene Complex Cp Mo(btt)MoCp : Radical and Diradical States.

Benzene-1,2,4,5-tetrathiolate (btt) has been used as a bridging ligand to prepare a redox active (molybdenocene dithiolene)-based bimetallic complex Cp Mo(btt)MoCp , which exhibits four successive electron transfers up to the tetracation. Spectro-electrochemical investigations together with DFT and TD-DFT calculations evidence that the two electroactive MoS C metallacycles are electronically coupled in the monocationic as in the dicationic state. Two salts of the dication [Cp Mo(btt)MoCp ] have been structurally characterized with PF and HSO counterions, showing different chair or boat conformations associated with variable folding angles of the two MoS C metallacycles along the S-S hinge.

Evaluation of tight-binding DFT performance for the description of organic photochromes properties.

Photochromic molecules are widely studied and developed for their many potential applications. To optimize the required properties through theoretical models, a considerable chemical space is to be explored, and their environment in devices is to be accounted for..