In this paper, a facile route was designed to prepare four new NLO polyaryleneethynylenes, which were constructed by two different chromophore moieties with the regular AB structure, to achieve a high NLO coefficient according to our recent work on ‘‘isolation chromophores’’. Meanwhile, normal aromatic rings or perfluoroaromatic rings were also introduced as isolation groups to investigate the aromatic/perfluoroaromatic (Ar–ArF) self-assembly effect in these NLO polymers. Thanks to the helpful self-assembly effect, the NLO effect and stability of P2, with perfluorophenyl groups as isolation groups, were improved to a large degree, in comparison with its analog P1 containing normal phenyl groups as isolation groups.
