D.V.Zhuzhelskii, E.G.Tolstopjatova, S.N.Eliseeva, A.V.Ivanov, ShouleiMiao, V.V.Kondratiev, Electrochemical properties of PEDOT/WO₃ composite films for high performance supercapacitor application, Electrochimica Acta, 2019, V.209, P.182-190. DOI: 10.1016/j.electacta.2019.01.007

Abstract

Tungsten oxide was electrochemically deposited from a metastable acidic solution of isopolytungstate on glassy carbon electrodes coated by the films of a conducting polymer poly-3,4-ethylenedioxythiophene (PEDOT). The formation of PEDOT/WO₃ composite films during electrochemical deposition of tungsten oxide into the polymer matrix was gravimetrically monitored by EQCM. The morphology of WO₃ deposits was studied using SEM, TEM and EDX analysis, including element mapping and depth concentration profile of main elements. SEM and TEM images of PEDOT/WO₃ composites show disperse distribution of WO₃ precipitates in the porous matrix of PEDOT, possessing high surface area and pore volume, effective for charge transport. Electrochemical behavior of PEDOT/WO₃ was investigated in 0.5 M H₂SO₄ by cyclic voltammetry, galvanostatic charge-discharge method and electrochemical impedance spectroscopy. The WO₃ component in the obtained PEDOT/WO₃ composite electrodes exhibited high specific capacitance of 689 F g⁻¹ in the potential range −0.3–0.0 V. The work presents a simple approach for the synthesis of PEDOT/WO₃ composites with high values of specific capacitance. The obtained results indicate that PEDOT/WO₃ composite could be a promising electrode material for supercapacitor applications.

Anton V. Rozhkov, Mariya A. Krykova, Daniil M. Ivanov, Alexander S. Novikov, Anna A. Sinelshchikova, Marina V. Volostnykh, Mikhail A. Konovalov, Mikhail S. Grigoriev, Yulia G. Gorbunova, Vadim Yurievich Kukushkin, Reverse Arene Sandwich Structures Based upon π‐hole•••[MII] (d8M = Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile, Angew. Chem. Int. Ed., Accepted Author Manuscript. DOI: 10.1002/ange.201814062

Abstract

The complexes [Pt(tpp)] (M = Pt; H2tpp = tetraphenyl‐porphyrin), [M(acac)2] (M = Pd, Pt, Hacac = acetylacetone), and [Pd(ba)2] (Hba = benzoylacetone) were co‐crystallized with highly electron‐deficient arene systems to form reverse arene sandwich structures built by π‐hole•••[MII] (d8M = Pt, Pd) interactions. The adduct [Pt(tpp)]•2C6F6 is monomeric, whereas the diketonate 1:1 adducts form columnar infinity 1D‐stack assembled by simultaneous action of both π‐hole•••[MII] and C–F interactions. The reverse sandwiches are based on noncovalent interactions and calculated ESP distributions indicate that in π‐hole•••[MII] contacts, [MII] plays the role of a nucleophile.

Kamran T.Mahmudov, Vadim Yu.Kukushkin, Atash V.Gurbanova, Mikhail A.Kinzhalov, Vadim P.Boyarskiy, M. Fátima C. Guedesda Silva, Armando J.L.Pombeiro, Isocyanide metal complexes in catalysis, Coordination Chemistry Reviews, 384, 65–89, 2019. DOI: 10.1016/j.ccr.2019.01.002

Abstract

The catalytic applications of isocyanide metal systems (from early to late transition metals) for organic transformations were systematically reviewed, and the studied transformations are also classified by type regardless of the metal center. A broad range of catalytic reactions of organic substrates has been developed including reactions of alkenes and alkynes, functionalization of E–H and E–E to multiple bonds, alkyl- and aryl-halides activation, nucleophilic addition, electron transfer catalysis, and photochemical reactions. This report gives a general overview of reaction routes, mechanisms, and driving forces and highlights the potential of isocyanide metal species, drawing attention to emerging putative targets.