Ethynylene and p-phenylene are frequently employed constitutional units in constructing the backbone of nanoscopic molecules with specific shape and mechanical or electronic function. How well these properties are defined depends on the flexibility of the backbone, which can be characterized via the end-to-end distance distribution. This distribution is accessible by pulse electron paramagnetic resonance (EPR) distance measurements between spin labels that are attached at the backbone. Four sets of oligomers with different sequences of p-phenylene and ethynylene units and different spin labels were prepared using polar tagging as a tool for simple isolation of the targeted compounds. By variation of backbone length, of the sequence of p-phenylene and ethynylene units, and of the spin labels a consistent coarse-grained model for backbone flexibility of oligo(p-phenyleneethynylene)s and oligo(p-phenylenebutadiynylene)s is obtained. The relation of this harmonic segmented chain model to the worm-like chain model for shape-persistent polymers and to atomistic molecular dynamics simulations is discussed. Oligo(p-phenylenebutadiynylene)s are found to be more flexible than oligo(p-phenyleneethynylene)s, but only slightly so. The end-to-end distance distribution measured in a glassy state of the solvent at a temperature of 50 K is found to depend on the glass transition temperature of the solvent. In the range between 91 and 373 K this dependence is in quantitative agreement with expectations for flexibility due to harmonic bending. For the persistence lengths at 298 K our data predict values of (13.8 ± 1.5) nm for poly(p-phenyleneethynylene)s and of (11.8 ± 1.5) nm for poly(p-phenylenebutadiynylene)s.

A novel series of homo‐, bi‐, and mononuclear Ni(II)‐based catalysts (BNCn n = 1–4, MNC4) were used for ethylene polymerization. The optimum conditions for the catalyst BNC4 (the highest catalytic activity) was obtained at [Al]/[Ni]=2000/1, Tp = 42 °C, and tp = 20 min that was 1073 g PE/mmol Ni h. In theoretical study, steric and electronic effects of substituents and diimine backbone led to prominent influence on the catalyst behavior. The highest MV was resulted from polymerization using BNC4; however, the highest unsaturation content was obtained from BNC1. GPC analysis showed a broad MWD (PDI = 17.8). BNC1 and BNC2 in similar structures showed broad peaks in DSC thermogram, while BNC3 and BNC4 with more electronic effects showed a peak along with a wide shoulder. Monomer pressure increasing showed enhancing in activity of the BNC4, meanwhile a peak with shoulder to a single peak in DSC thermogram and uniformity in morphology of the resulted polymer were observed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3000–3011

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