Recent Advances in Polyallenes: Preparation, Self‐Assembly, and Stimuli‐Responsiveness

Abstract

Polyallenes, as a typical type of reactive polymers, are of great significance and have aroused widespread interest because they contain double bonds that can be post‐modified into other functionalities to afford varieties of functional materials. This Minireview firstly highlights the recent advances in the preparation of polyallenes, including preparation of helical polyallenes through directly polymerization of chiral allene monomers or helix‐sense‐selective polymerization (HSSP) of achiral allene monomers, synthesis of 1,2‐regulated polyallenes and 2,3‐regulated polyallenes via selective polymerization of allene monomers, polymerization of allene monomers catalyzed by Ni(II)‐terminated poly(3‐hexylthiophene) (P3HT), and so on. Then, latest progress on the self‐assembly and stimuli‐responses of polyallene‐based diblock, ABA and ABC triblock copolymers is summarized. We hope this Minireview will inspire more interest in developing polyallenes and encourage further advances in functional materials.

Synthesis of air‐stable poly(benzonorbornadiene)s via ring‐opening metathesis polymerization

“…and Ru-catalyzed metathesis polymerizations 12,[23][24][25][26] are the representative polymerizations to afford functional polymers with high functional group tolerance in mild conditions. Recently, highly functionalized polymers with structural advantages are reported by using various transition-metal catalysts such as controlled synthesis of helical polymers, [27][28][29][30][31] brush polymers, 32 polyallenes, 33 and polycarbenes. 34 Selective oxidation of allylic and/or benzylic C H bonds readily occurs under mild conditions via easy generation of stable radicals.…”

Recent advances in the metal-catalyzed asymmetric synthesis of chiral allenes

“…Notably, axial chiral allenes exist widely in advanced functional materials, bioactive pharmaceuticals and natural products. 1 As illustrated in Fig. 1A, laballenic acid is a natural product of seed oil and citroside A is isolated from the aerial parts of Cirsium setosum .…”

Thermotropic chirality enhancement of nanoparticles constructed from foldamer/bis(amino acid) complexes

“…Artificial foldamers are often used to construct chiral materials because they can fold into a compact helical conformation, [16][17][18][19] which is stabilized by non-covalent interactions such as solvophobic interactions and π-π stacking interactions in the foldamer main chain. 20,21 In particular, they can undergo a conformation transition in response to temperature. 22 An oligo(m-phenylene ethynylene) possessing chiral tri(ethylene glycol) monomethyl ether pendants exhibits helix-coil transition because the π-π stacking interaction in the main chain is weakened when the temperature increases from −10 to 70 °C, giving rise to decreased CD intensity.…”