1H and13C NMR Full Assignment of a Series of Precursor Polymers Derived from the Sulfinyl Route Towards Poly(p-phenylene vinylene)

Identification and Quantification of Polymerization Defects in 13C-Labeled Sulfinyl and Gilch OC1C10−PPV by NMR Spectroscopy

“…Since only oligomers were formed due to steric hindrance of the two sulfoxide groups, we were able to observe the end group resonances (-CH 2 S(O)R). If we take the influence of electron donating substituents on the aromatic system of OC 1 C 10 -PPV into account, 10 the complete absence of signals in the region between 52 and 40 ppm for the sulfinyl polymer is a strong confirmation that in the sulfinyl route no tail-to-tail additions occur. Concerning the carbonyl resonances, it must be noticed that the Gilch polymer has two carbonyl functionalities, an aldehyde resonance at 188.9 ppm and a carboxylic acid resonance at 165.2 ppm, while the sulfinyl polymer has only one carbonyl resonance at 188.9 ppm.…”

“…The presence of the asymmetric carbon atom 8 in combination with the asymmetric sulfoxide group results in four diastereomers of which two pairs, RR and SS on one hand and RS and SR on the other hand, can be differentiated by NMR. 26 The splitting of the carbon 8 (58.4 and 57.3 ppm) represents the population distribution of these two pairs of isomers and explains the resultant splitting of the carbon 7 resonance (31.0 and 29.0 ppm) in equal (integration) parts. The correspond- ing proton resonances were assigned by means of an one-bond optimized HETCOR experiment on the eliminated polymer (Figure 3), which shows that the resonances of carbon atom 8 are correlated with a proton signal around 5.2 ppm, while the resonances of carbon 7 are correlated with a proton resonance around 3.7 ppm.…”

“…6,9 Over the last years, a new and promising precursor route toward this and other PPV-based polymers, was developed in our laboratory, the so-called sulfinyl route. 8,10 This route is distinguished from the other routes because it starts from an asymmetric monomer, i.e., where the leaving group (Cl) and polarizer group (S(O)R) are different. On the other hand, in the Gilch and most other precursor routes, the polarizer and leaving groups are identical.…”

Step Polymerization

“…2-229). These [Cho, 2002;Kraft et al, 1998;Lenz et al, 1988;van Breemen et al, 2001]. PPV can also be synthesized by the Heck coupling of aryl halides with alkenes (Eq.…”

Complete assignment of 19F, 1H and 13C NMR spectra of monomers and precursors towards bridge trifluoromethylated poly(p‐phenylenevinylene)

“…Also, it will allow the detection of any evidence of diastereoselectivity during the polymerization process. 26 The NMR assignments will also be important in the analysis of the subsequent thermal elimination step resulting in conjugated trifluoromethylated PPV polymers.…”