The first synthesis and new properties of regioregular, head-to-tail coupled polythiophenes

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

“…Since this reaction requires commercially available Grignard compounds and can be conducted at room temperature, it marked a major advance in comparison to the previously reported methods where cryogenic temperatures were used. [59,60] In 2004/2005 McCullough and coworkers [21,22] and Yokozawa and coworkers [23,24] independently reported that the GRIM polymerization involves a chain-growth but not a step-growth mechanism. A unique intramolecular catalyst-transfer process was found to be responsible for the chain-growth propagation.…”

Advanced Functional Regioregular Polythiophenes

“…The cross-coupling polymerization of these intermediates occurs without any scrambling. The resulting rrP3ATs afford HT-HT regioregularity of 98-100% as seen by NMR study, and the number averaged molecular weights (M n ) are typically 20-40 K with polydispersities (PDI) of around 1.4 [20,22,48,57,58]. This procedure was later modified by replacing MgBr 2 ·Et 2 O with ZnCl 2 , thus allowing for greater solubility of the reactive intermediate at cryogenic temperatures.…”

“…Atomic force microscopy (AFM) is typically used to observe the morphology in film. McCullough et al were the first to show the supramolecular ordering of self-assembled rrP3ATs by X-ray study [22,49,57,88]. X-ray data of an rrP3HT film prepared by simple evaporation of xylene solution on a glass slide showed strong intensity in three small-angle reflections, <100>, <200>, and <300> peaks, corresponding to a well-ordered lamellar structure with an interlayer spacing of 16.0Å.…”

New Materials Derived from Heterocyclic Systems

“…For example, a polymer with R ¼ CH 2 O (CH 2 ) 2 O(CH 2 ) 2 OCH 3 has been prepared with very high regioselectivity by McCullough [115], showing, to the best of our knowledge, the highest conductivity reported for a polythiophene.…”