Rechargeable batteries that use organic matter as the capacity-carrying material have previously been considered a technology for the future. Earlier batteries in which both the anode and cathode consisted of organic material required significant amounts of conductive additives and were often based on metal-ion electrolytes containing Li or Na. However, we have used conducting poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with anthraquinone (PEDOT-AQ) or benzonquinone (PEDOT-BQ) pendant groups as the negative and positive electrode materials, respectively, to make an all-organic proton battery devoid of metals. The electrolyte consists of a proton donor and acceptor slurry containing substituted pyridinium triflates and the corresponding pyridine base. This slurry allows the 2e/2H quinone/hydroquinone redox reactions while suppressing proton reduction in the battery cell. By using strong (acidic) proton donors, the formal potential of the quinone redox reactions is tuned into the potential region in which the PEDOT backbone is conductive, thus eliminating the need for conducting additives. In this all-organic proton battery cell, PEDOT-AQ and PEDOT-BQ deliver 103 and 120 mAh g, which correspond to 78% and 75%, respectively, of the theoretical specific capacity of the materials at an average cell potential of 0.5 V. We show that PEDOT-BQ determines the cycling stability of the device while PEDOT-AQ provides excellent reversibility for at least 1000 cycles. This proof-of-concept shows the feasibility of assembling all-organic proton batteries which require no conductive additives and also reveals where the challenges and opportunities lie on the path to producing plastic batteries.

A new qualitative model for estimating the properties of substituted cyclopentadienes and siloles in their lowest ππ* excited states is introduced and confirmed through quantum chemical calculations, and then applied to explain earlier reported experimental excitation energies. According to our model, which is based on excited-state aromaticity and antiaromaticity, siloles and cyclopentadienes are cross-hyperconjugated "aromatic chameleons" that adapt their electronic structures to conform to the various aromaticity rules in different electronic states (Hückel's rule in the π(2) electronic ground state (S0) and Baird's rule in the lowest ππ* excited singlet and triplet states (S1 and T1)). By using pen-and-paper arguments, one can explain polarity changes upon excitation of substituted cyclopentadienes and siloles, and one can tune their lowest excitation energies by combined considerations of ground- and excited-state aromaticity/antiaromaticity effects. Finally, the "aromatic chameleon" model can be extended to other monocyclic compound classes of potential use in organic electronics, thereby providing a unified view of the S0, T1, and S1 states of a range of different cyclic cross-π-conjugated and cross-hyperconjugated compound classes.

Increased steric bulk in norbornadienes with application in solar energy storage leads to higher quantum yields, red-shifted absorption and higher thermal stability.

Electrodes based on organic matter operating in aqueous electrolytes enable new approaches and technologies for assembling and utilizing batteries that are difficult to achieve with traditional electrode materials.H ere,w er eport howthiophene-based trimeric structures with naphthoquinone or hydroquinone redox-active pendent groups can be processed in solution, deposited, dried and subsequently polymerized in solid state to form conductive (redox)p olymer layers without any additives.S uchp ost-deposition polymerization offers efficient use of material, high mass loading (up to 10 mg cm À2 )and good flexibility in the choice of substrate and coating method. By employing these materials as anode and cathode in an acidic aqueous electrolyte arocking-chair proton battery is built. The battery shows good cycling stability (85 % after 500 cycles), withstands rapid charging,with full capacity (60 mAh g À1 )r eached within 100 seconds,a llows for direct integration with photovoltaics,a nd retains its favorable characteristics even at À24 8 8C.

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Crossing a barrier: Molecules with saturated ER2 units (E=C or Si, R=electron‐releasing group) inserted between two π‐conjugated segments have electronic and optical properties that resemble those of cross‐conjugated molecules (see figure). This cross‐hyperconjugation provides a deeper understanding of the conjugation phenomenon, and is an alternative to cross‐conjugation in the design of molecules for nano and materials applications.

Recently there has been much interest in electron transfer and transport through cross-conjugated molecules as interesting test cases for the interplay between molecular and electronic structure as well as potential motifs in the design of new compounds for molecular electronics. Herein we expand on this concept and present the synthesis and characterization of a series of four organic mixed-valence dyads to probe the effect of the bridge structure on the electronic coupling. The electronic coupling between two triarylamine units could be mediated either by cross-hyperconjugation through a saturated ER 2 bridge (E ¼ C or Si, R ¼ alkyl or silyl group), or via a cross-conjugated p-system. The aim of the study is to compare the electron transfer through the various saturated bridges to that of a cross-p-conjugated bridge. The electronic coupling in these mixed-valence compounds was determined by analysis of intervalence charge transfer bands, and was found to be in the range of 100-400 cm À1 . A complementary DFT and TD-DFT study indicated that the electronic coupling in the dyads with saturated ER 2 segments is highly conformer dependant. Furthermore, the calculations showed that two types of interactions contribute to the electronic coupling; a through-bond cross-(hyper)conjugation mechanism and a through-space mechanism. Taken together, these findings suggest the possibility for new architectures for molecular electronics applications utilizing cross-hyperconjugation through properly selected saturated segments which have comparable electron transfer characteristics as regular cross-p-conjugated molecules.

M. et al. (2014) 1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation. Table-of-contentsThe fusion of two cross-hyperconjugated segments in form of the small 1,4-disilacyclohexa-2,5-diene cycle provides for electronic and optical properties which resemble to those of π-conjugated cycles.2 Abstract: The electronic structures of 2,3,5,6-tetraethyl-1,4-disilacyclohexa-2,5-dienes with either four chloro (1a), methyl (1b), or trimethylsilyl (TMS) (1c) substituents at the two silicon atoms were examined in an effort to design cyclic compounds with strong neutral cross-hyperconjugation between π-and σ-bonded segments. Remarkable variations in the lowest electronic excitation energies, lowest ionization energies, and the first oxidation potentials were observed upon change of substituents, as determined by gas phase ultraviolet 3