Unexpectedly flexible graphene nanoribbons with a polyacene ladder skeleton

A new conjugated ladder polymer with a polyacene skeleton was synthesized in a Aldol-type condensation protocol between benzylic and aryl-ketone side groups of suitably functionalized single-stranded presursor polymers. The photophysical...

Tailoring π-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers

The development of synthetic strategies to engineer π-conjugated polymers is of paramount importance in modern chemistry and materials science. Here we introduce a synthetic protocol based on the search for specific vibrational modes through an appropriate tailoring of the π-conjugation of the precursors, in order to increase the attempt frequency of a chemical reaction. First, we design a 1D π-conjugated polymer on Au(111), which is based on bisanthene monomers linked by cumulene bridges that tune specific vibrational modes. In a second step, upon further annealing, such vibrational modes steer the twofold cyclization reaction between adjacent bisanthene moieties, which gives rise to a long pentalene-bridged conjugated ladder polymer featuring a low bandgap. In addition, high resolution atomic force microscopy allows us to identify by atomistic insights the resonance form of the polymer, thus confirming the validity of the Glidewell and Lloyd´s rules for aromaticity. This on-surface synthetic strategy may stimulate exploiting previously precluded reactions towards π-conjugated polymers with specific structures and properties.

Impact of Alternative Stabilization Strategies for the Production of PAN-Based Carbon Fibers with High Performance

The aim of this work is to review a possible correlation of composition, thermal processing, and recent alternative stabilization technologies to the mechanical properties. The chemical microstructure of polyacrylonitrile (PAN) is discussed in detail to understand the influence in thermomechanical properties during stabilization by observing transformation from thermoplastic to ladder polymer. In addition, relevant literature data are used to understand the comonomer composition effect on mechanical properties. Technologies of direct fiber heating by irradiation have been recently involved and hold promise to enhance performance, reduce processing time and energy consumption. Carbon fiber manufacturing can provide benefits by using higher comonomer ratios, similar to textile grade or melt-spun PAN, in order to cut costs derived from an acrylonitrile precursor, without suffering in regard to mechanical properties. Energy intensive processes of stabilization and carbonization remain a challenging field of research in order to reduce both environmental impact and cost of the wide commercialization of carbon fibers (CFs) to enable their broad application.

Carbonization of single polyacrylonitrile chains in coordination nanospaces

Accommodation of polyacrylonitrile in MOFs facilitated and regulated the transformation to ladder polymer in the carbonization process.

Switching of the conformational flexibility of a diazacyclooctane-containing ladder polymer by coordination and elimination of a Lewis acid

We report the first system of ladder polymers capable of interconversion between rigid and flexible conformations by coordination and elimination of a Lewis acid (BPh2Cl) on diazacyclooctane units in the main chain.