We demonstrate a facile synthetic route to functional disubstituted polyacetylenes bearing highly polar groups based on polymer reactions. A pentafluorophenyl (PFP) ester-containing diphenylacetylene was designed and polymerized to obtain PFP activated ester-functionalized disubstituted polyacetylene (P1). P1 was used as a parent polymer to further react separately with diverse amines, giving rise to a series of functional disubstituted polyacetylenes with a chiral moiety and hydroxyl and carboxyl groups in high yields under mild condition. Spectral characterization data indicated that the polymers' structures were well consistent with the expected results. The helicity and emission property of polymers were also studied.

The research on self-healing polymers has been a hot topic. The encapsulated-monomer/catalyst, supramolecular self-assembly, and reversible or dynamic covalent bond formation are the prevailingly adopted strategies. The alternative of irreversible covalent bond formation is, however, to be further developed. In this contribution, self-healing hyperbranched poly(aroyltriazole)s of PI and PII sharing such mechanism were developed. The polymers were synthesized by our developed metal-free click polymerizations of bis(aroylacetylene)s and triazide. They are processible and have excellent film-forming ability. High quality homogeneous films and sticks free from defects could be obtained by casting. The scratched films could be self-repaired upon general heating. The cut films and sticks could be healed by stacking or pressing the halves together at elevated temperature. Thus, these hyperbranched polymers could find broad applications in diverse areas, and our design concept for self-healing materials should be generally applicable to other hyperbranched polymers with reactive groups on their peripheries.

Perylene bisimide derivatives substituted with one and two tetraphenylethene moieties at 1 and 1,7-postions show distinct optical properties. The former displays characteristic emission features of perylene bisimides in solution and red emission in the aggregate state, while the latter is nonemissive in solution but highly red-emissive in the aggregate state.

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Pentafluorophenyl (PFP) ester-functionalized poly(phenylacetylene)s (PPAs, P1, P2, and P3) were designed and synthesized in desirable yields and molecular weight by using organorhodium complexes as catalysts. Furthermore, these PFP-containing PPAs were used as precursors to prepare a series of mono- and dual-functionalized PPAs by the substitution of the activated ester moieties with functional amines. The structures of the PFP-containing PPAs and the derived functional PPAs were characterized by using multiple spectroscopic techniques including GPC, FTIR, 1H NMR, 13C NMR, and 19F NMR. The experimental details and the characterization data demonstrate that activated ester synthetic route to functional PPAs is facile (just stirring the precursor polymer with proper amine(s) at room temperature for hours), efficient (complete transition from ester to amide has been confirmed), and quantitative (the relative content of a specific functionality can be precisely preset by controlling the feed ratio of the functional amines). By reacting three PFP-containing PPAs with chiral amines or with chiral and nonchiral alkyl amines in a step-by-step way, a series of seven different PPAs with asymmetric carbon in the side chains were obtained. CD measurements indicated that the incorporation of chiral amine into polymer side chains induced helicity formation of P1 backbone. P1-C*Ph(L) and P1-C*Ph(D) backbones adopt predominantly right-handed and left-handed helical conformation, respectively. While the flexible spacer between the chiral center and the rigid PPA backbone blocked the induction of main-chain helicity by chiral pendants, thus no CD signals were recorded for P2-C*Ph(L) and P3-C*Ph(L). Substitution of PFP ester with amine-functionalized PEGs transited the hydrophobic PPAs to hydrophilic. All of the PEG-containing PPAs can be dissolved in water and form clear solutions. Meanwhile, all of the aqueous solutions exhibit LCST behavior and the hydrophilic PEG chains and hydrophobic alkyl spacers have positive and negative impact on the cloud point, respectively. Contact angles measurements showed that the length and content of the PEG chains contribute greatly to the hydrophilic property, and the length of the alkyl spacers and the content of the alkyl amine component played a contrary role. By controlling the ratio of the PEGylated and alkyl amines, the amphiphilic property of the PPAs can be well tailored.