Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom

Abstract

The original synthetic strategy for a new type of poly(arylene vinylene) (PAV) is presented, where the CC-bondforming coupling of bis(alkoxycarbonyldiazomethyl)aromatic compounds is utilized as propagation. The strategy is unique in that the resulting PAVs have an alkoxycarbonyl group as an electron-withdrawing substituent on each vinylene carbon atom in the polymer main chain. Among the transition-metal catalysts examined in this study, RuCl(cod)Cp* (cod = 1,5-cyclooctadiene, Cp* = pentamethylcyclopentadienyl) is the most efficient, affording PAVs from a series of bis(alkoxycarbonyldiazomethyl)aromatic compounds with a high trans-CC-forming selectivity of up to 90%. A PAV sample with a fluorenylene framework as an arylene moiety prepared by the Ru catalyst exhibited a hole mobility of 4 × 10 −6 cm 2 V −1 s −1 .

Direct and selective access to amino-poly(phenylene vinylenes)s with switchable properties by dimerizing polymerization of aminoaryl carbenes

“…Formal polymerization by dimerization of non-heteroatom-stabilized bis-(aryl)carbenes, generated by decomposition of corresponding bis-diazo compounds, has also been reported 33 – 36 . Depending on the nature of the catalyst, either poly(phenylene vinylene)s (PPV’s) or poly(aryl azine)s could be achieved, upon extrusion or retention of N 2 , respectively.…”

New classes of functionalized parylenes and poly(phenylene vinylene)s via coupling of dihaloxylyl diesters

“…Our hypothesis was that the dimerization of a reduced (i.e., dehalogenated) form of the compound should result in the formation of a PPX whereas condensation followed by elimination would afford a PPV. 28,29 An intrinsic advantage of such an approach is that it enables the modification of the ethylene or vinylene repeat units and, as such, can be expected to more profoundly influence the intrinsic chemical, optoelectronic and other properties displayed by the polymers, particularly when compared to approaches that entail arene modifications or are relatively distal to the main chains. Moreover, the precursor is commercially available and can be readily adapted through esterification with various alcohols which should facilitate the integration of PPV and PPX in a broader range of applications and enable more detailed studies of the fundamental properties displayed by these polymeric materials.…”

Palladium-catalyzed carbene coupling polymerization: synthesis of E-poly(arylene vinylene)s

“…2 There are currently four major synthetic methods already established, namely precursor routes, 3 nucleophilic polycondensation, 4 olefin metathesis polymerization, 5 and palladium-catalyzed C–C coupling polymerization. 6 For the synthesis of PAVs, the interesting topics include the precise control of the vinylene configuration, 7 and the introduction of EWGs on arylene or vinylene, 8 which significantly affect the physical and chemical properties of the resultant polymers.…”

“…It has been known that the introduction of electron-withdrawing groups onto the arylene rings or the vinyl units can reduce the barrier of electron injection. 8 Therefore, we further proceeded to synthesize CF 3 -substituted PAVs, on the basis of our previous report on Pd-catalyzed cross-coupling of benzyl bromide with CF 3 -substituted diazo compounds or N -tosylhydrazones. 12 Initially, we failed to obtain the corresponding polymer product by the reaction using A1 with bis( N -tosylhydrazone) of trifluoroacetophenone under the standard conditions.…”