The Amidinium–Carboxylate Salt Bridge as a Proton‐Coupled Interface to Electron Transfer Pathways

Abstract

Due to the tolerance of catalyst 7 in combination with the interesting properties of poly(DCPD), new filled or unfilled thermosets could be prepared, which should find novel applications in the field of electro casting, insulation, and tooling (among others) in the near future. Work to improve catalysts and polymer systems are ongoing. Experimental SectionThe ruthenium and osmium complexes were prepared according to literature procedures [ll]. NBE was purchased from Fluka, and DCPD (technical quality, 94%) from Shell and used as received. Viscosimetric measurements were performed on a home-built, real-time viscosimeter. Gel times were recorded on a Brookfield viscosimeter, DSCs on a Mettler DSC30 with a Mettler TCll controller, TGAs on a Mettler TG50 with a Mettler TCfOA controller, and surface roughness on a Form Talysurf S3C-50. Micro hardness was determined on a Fischerscope H100. I3C CP-MAS NMR spectra of a piece of poly(DCPD) that was tightly fitted into the spinner were recorded on a Bruker 400-MHz instrument with a MAS rate of 11 kHz and a pulse delay of 5 s (a pulse delay of 60 s gave an identical result).

Molecular Networks Forming Crystalline and Liquid Crystalline Phases by Combined Hydrogen-Bonding and Ionic Interactions

“…The length of the dinuclear molecular complex estimated using Hyperchem software is about 22 Å, in good agreement with the data reported for the complex of bis(cyclic amidine) with 4-methylbenzoic acid 10 . Apparently, this length is considerably higher than the obtained thickness of the polar sublayer by about 5 Å.…”

Proton-coupled electron transfer: the mechanistic underpinning for radical transport and catalysis in biology

“…PCET is triggered by laser excitation of the donor or acceptor and resolved kinetically by performing time-resolved spectroscopy. These systems have provided tangible kinetics benchmarks for PCET reactions (Turró et al 1992; Kirby et al 1995Kirby et al , 1997Roberts et al 1995Roberts et al , 1997Deng et al 1997;Yeh et al 2001b;Damrauer et al 2004) and stimulated the development of theories to describe PCET (Cukier & Nocera 1998;Hammes-Schiffer 2001a,b).…”

Proton-Coupled Electron Transfer

“…In this review, we outline our recent theoretical (15)(16)(17)(18) and experimental (19)(20)(21)(22)(23)(24) efforts aimed at a systematic study of the coupling between proton and electron transfer, which we refer to as proton-coupled electron transfer (PCET). The work has been directed toward understanding PCET in biomimetic systems, where the potential for this coupling can be assessed in a systematic manner.…”

“…The desire to explore PCET in a well-defined geometry motivated the synthesis of model compounds that preserve the features of charge separating networks in biological systems and permit the interrogation of the electron and proton dynamics (19)(20)(21)(22)(23)(24). The key to the approach is to photoinduce electron transfer within a fixed-distance donor/acceptor pair that has a proton transfer network internal to the electron transfer pathway.…”