Polymeric Composites Based on Polysilanes for Plastic Electronics

Nešpůrek, S.; Pospíšil, J.; Kratochvílová, Irena; Sworakowski, J.

doi:10.1080/15421400801904682

Cited by 4 publications

(3 citation statements)

References 52 publications

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“…The B3LYP method usually provides reliable ground‐state molecular conformations, infrared vibrational spectra, and energies at moderate computational costs. It has been successfully used for the conformation study of many different conjugated systems 24–32. Moreover, this method was also chosen with regard to the fact that the hydrogenated PPDP molecule is an open‐shell system.…”

Section: Theoretical Studymentioning

confidence: 99%

Study of phenylpyridyldiketopyrrolopyrrole interaction with hydrogen in gas and in acids

Salyk

Vyňuchal

Kratochvílová

et al. 2010

Physica Status Solidi (a)

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In this work, we applied experimental and theoretical techniques to study the influence of hydrogenation on the electrical properties of a derivative of diketodiphenylpyrrolopyrrole – phenylpyridyldiketopyrrolopyrrole (PPDP). From the experimental results and theoretical models it follows that the suitable reaction of PPDP with hydrogen can modulate the material electronic properties (ionization potential (IP), surface potential, conductivity).

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Section: Theoretical Studymentioning

confidence: 99%

Study of phenylpyridyldiketopyrrolopyrrole interaction with hydrogen in gas and in acids

Salyk

Vyňuchal

Kratochvílová

et al. 2010

Physica Status Solidi (a)

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“…Furthermore, such compounds are of general interest in chemistry as the closest analogues of organic compounds, for which catenation and the presence of C–C bonds are typical. They are also of practical interest due to their specific electronic and redox properties, − promising for photonics, microelectronics, molecular wires design, − etc. As the Si–Si bond is more labile than the C–C bond, redox catalysis may be broadly applicable in this molecular family.…”

Section: Introductionmentioning

confidence: 99%

Redox Upconversion and Electrocatalytic Cycles in Activation of Si–Si Bonds: Diverging Reactivity in Hole- and Electron-Catalyzed Transformations

Balycheva,

Chabuka,

Kuhn

et al. 2024

J. Phys. Chem. C

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Electron transfer is a powerful tool for promoting chemical reactions. A subset of redox-mediated transformations are "electroneutral" reactions, where the reactant and product are in the same oxidation state. In such processes, electrons (or holes) can serve as genuine catalysts if the products have higher reduction (or oxidation) potential than the reactants, i.e., in the presence of electron (or hole) upconversion. This work explores the differences between electron and hole catalysis in redox-activated transformations of the same substrate. We show that for redox upconversion to occur in both the reductive and oxidative modes, the reduced and oxidized reactions must follow different paths. The chosen substrate, 1,2-disila-3,5-cyclohexadiene 1, combines an electron-rich π-system with a Si−Si bond and can undergo Si−Si bond scission in both the oxidative and reductive regimes. Single-electron oxidation with a molecular oxidant leads to the formation of a radical cation that undergoes an intramolecular rearrangement with the elimination of dimethylsilylene and the formation of a radical cation of silole, 2. The latter can oxidize another molecule of neutral reactant 1, a step that closes the hole catalytic cycle. The unique utility of the radical-cationic reactivity mode is illustrated by the lack of hole upconversion under electrochemical conditions, where the radical-cationic reaction path is aborted by further oxidation at the electrode. In contrast, the radical anion formed from one-electron reduction of 1 is unreactive. This persistent species can be formed reversibly in THF, both chemically and electrochemically. Its reactivity can be unlocked by the addition of stoichiometric amounts of water. Although the subsequent reaction also involves Si−Si bond cleavage, it follows a path that is different from that of the radical-cationic version. Interestingly, electrochemical experiments clearly confirm that this process is also a chain reaction that requires a catalytic amount of electrons (0.3 equiv) for the complete conversion of the substrate. Computations identify a possible mechanistic pathway to the observed products and support the importance of reductant upconversion in this electron-catalyzed process. Hence, this work identified the first molecular system that can undergo true electron-catalyzed and hole-catalyzed processes and confirmed that these processes lead to different products.

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“…Polysilanes1 have attracted considerable attention due to their usefulness as precursors for thermally stable ceramics2, 3 or materials for microlithography4, 5 and also due to their potential in the preparation of new types of materials showing semiconducting, photoconducting or nonlinear optical properties 6–8. In spite of the growing interest in polysilanes,9, 10 their methods of preparation are still limited. They have been traditionally prepared by the condensation of dichlorosilanes with alkali metals (Wurtz‐type condensation).…”

Section: Introductionmentioning

confidence: 99%

Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

Ishifune

Sana

Ando

et al. 2011

Polymer International

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The electroreductive polymerization of dichloromethylphenylsilane in the presence of triphenylsilyl group-containing disilanes such as hexaphenyldisilane followed by the electroreductive termination with chlorotriphenylsilane afforded triphenylsilyl group-terminated polymethylphenylsilane in 15-32% yield. The isolated polymethylphenylsilane (M n = 3350 g mol −1 , M w /M n = 1.4) was found to react as a macroinitiator to copolymerize with dibutyldichlorosilane under electroreductive conditions producing the corresponding block copolymer (M n = 4730 g mol −1 , M w /M n = 1.2) in 38% yield. The ratio of monomer units (-MeSiPh-to-BuSiBu-) of the copolymer was determined to be 75 : 25 using 1 H NMR analysis, which was in good agreement with the calculated ratio (74 : 26) on the assumption that molecular weight of the macroinitiator was not changed. The block structure of the resulting copolymer, poly(methylphenylsilane)-block-poly(dibutylsilane), was also confirmed by comparing its 1 H NMR and UV absorption spectra with those of polymethylphenylsilane, polydibutylsilane and a statistical copolymer prepared by electroreductive polymerization of dichloromethylphenylsilane with dibutyldichlorosilane. This method is applicable to the preparation of other types of macroinitiator such as triphenylsilyl group-terminated polydibutylsilane, and polydibutylsilane-block-polymethylphenylsilane was also obtained using this macroinitiator.

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Polymeric Composites Based on Polysilanes for Plastic Electronics

Cited by 4 publications

References 52 publications

Study of phenylpyridyldiketopyrrolopyrrole interaction with hydrogen in gas and in acids

Study of phenylpyridyldiketopyrrolopyrrole interaction with hydrogen in gas and in acids

Redox Upconversion and Electrocatalytic Cycles in Activation of Si–Si Bonds: Diverging Reactivity in Hole- and Electron-Catalyzed Transformations

Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

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