Stereoretentive Ring-Opening Metathesis Polymerization to Access All-cis Poly(p-phenylenevinylene)s with Living Characteristics

Abstract

Poly(p-phenylene vinylene)s (PPVs), a staple of the conductive polymer family, consist of alternating alkene and phenyl groups in conjugation. The physical properties of this organic material are intimately linked to the cis/trans configuration of the alkene groups. While many synthetic methods afford PPVs with alltrans stereochemistry, very few deliver the all-cis congeners. We report herein the first synthesis of all-cis PPVs with living characteristics via stereoretentive ring-opening metathesis polymerization (ROMP). Exquisite catalyst control allows for the preparation of homopolymers or diblock copolymers with perfect stereoselectivity, narrow dispersities, and predictable molecular weights. All-cis PPVs can then serve as light-responsive polymers through clean photoisomerization of the stilbenoid units.

On‐Surface Debromination of 2,3‐Bis(dibromomethyl)‐ and 2,3‐Bis(bromomethyl)naphthalene: Dimerization or Polymerization?

“…Poly(p-arylene vinylenes) have been amply studied in terms of their extended conjugation and effective conjugation length which features have been essential for an understanding of their photophysical properties. [11,12,[14][15][16][17][18][19][20][21][22][23]41] A comparison with the corresponding ortho-analogues will have to consider, in particular, the effect of steric hindrance upon conjugation and chain conformation. For understand- Angewandte Chemie ing the electronic structure of poly(o-naphthylene vinylene) (4), STS measurements were conducted (see Figure 4i).…”

A Brief Review on Fundamentals of Conductive Polymer (CPs)

“…PPV is exceptionally glasslike, precisely solid and naturally steady. The conductivity is improved by doping with iodine, ferric chloride, soluble base metals or acids however with less steadiness [25,[26][27][28][29][30] .…”

Stereoretentive Olefin Metathesis: A New Avenue for the Synthesis of All-cis Poly(p-phenylene vinylene)s and Stereo­defined Polyalkenamers

“…In contrast, the stereoretentive catalyst Ru-2f provided perfect cis selectivity within the limits of sensitivity of 1 H NMR spectroscopy (entry 4). 42 The promising stereoselectivity established with Ru-2f prompted us to investigate the kinetics of the polymerization of 8, because only the polymerization of dicyclopentadiene 43 had previously been reported with this catalyst. Predictable molar masses of up to 13.1 kg/mol were obtained by varying the ratio of monomer to catalyst, and low dispersities (~1.1) were observed in all cases (Table 1).…”