In this work, air-stable palladium(II) catalysts bearing bidentate phosphine ligands were designed and prepared, which could initiate fast and living polymerizations of various diazoacetate monomers under mild conditions. The polymerization afforded the desired polymers in high yields with controlled molecular weights (M n s) and narrow molecular weight distributions (M w /M n s). The M n s of the isolated polymers were linearly correlated to the initial feed ratios of monomer to catalyst, confirming the living/controlled manner of the polymerizations. The M n also increased linearly with the monomer conversion, and all of the isolated polymers showed narrow M w /M n s. The polymerization was relatively fast and could be accomplished within several minutes. Such fast living polymerization method can be applied to a wide range of diazoacetate monomers in various organic solvents at room temperature in air. Taking advantage of the living nature, we facilely prepared a series of block copolymers through chain extension reactions. The amphiphilic block copolymers synthesized by this method exhibited interesting self-assembly properties. Moreover, polymerization of achiral bulky diazoacetate by Pd(II) catalysts bearing a chiral bidentate phosphine ligand leads to the formation of polymers with high optical activity due to the formation of the predominantly one-handed helix of the main chain. The helix sense of the polymers was determined by the chirality of the Pd(II) catalysts.

Self-sorting playsacrucial role in living systems such as the selective assembly of DNAa nd specific folding of proteins.However,the self-sorting of artificial helical polymers such as biomacromolecules has rarely been achieved.I nt his work, single-handed helical poly(phenyl isocyanide)s bearing pyrene (Py) and naphthalene (Np) probes were prepared, which exhibited interesting self-sorting properties driven by both helicity and molecular weight (M n)insolution, solid state, gel, and on the gel surface as well. The polymers with the same helix sense and similar M n can self-sort and assemble into welldefined two-dimensional smectic architectures and form stable gels in organic solvents.I nc ontrast, mixed polymers with opposite handedness or different M n were repulsive to each other and did not aggregate.M oreover,t he gels of helical polymers with the same handedness and similar M n can recognizet hemselves and adhere together to form ag el.

Controlled synthesis of bottlebrush polymers with high grafting density and carrying polymeric side chains on every backbone atom remains a great challenge. In this work, a series of well-defined poly­(l-lactic acid) (PLLA) and poly­(d-lactic acid) (PDLA) bearing polymerizable phenyl isocyanide on chain ends were prepared. Polymerization of the terminal phenyl isocyanide of these macromonomers by an alkyne-palladium­(II) catalyst yielded bottlebrush polymers carrying PLLA or PDLA side chains on every backbone atom. The grafted side chains were directly packed together without separating from other atoms. The polymerizations were proceeded in a living/controlled manner, and the degree of polymerization could be up to 250. The chiral macromonomers induced an asymmetric polymerization and resulted in a poly­(phenyl isocyanide) backbone with a preferred one-handed helix and large optical activity. Remarkably, the densely grafted bottlebrush polymers exhibited intriguing photoluminescence, although the macromonomers and poly­(phenyl isocyanide) backbone were all nonluminescent. Moreover, the preferred one-handed helix of the backbone induced clear circularly polarized luminescence (CPL) with defined handedness and a tunable dissymmetric factor.

In this manuscript, we designed and synthesized three core cross-linked micelles (M-5L, P-5L, and P-5D) with redox-responsive disulfide bonds in the core and carrying optically active helical polyisocyanide arms. Their arms were different in the helicity of the main chain and the chirality of the side groups. These micelles showed excellent redox-responsiveness to reducing agent. However, because of the different chiralities of the arms, the three micelles exhibited different performances in drug delivery and controlled release. The M-5L micelle carrying left-handed helical arms showed better therapeutic effect than the other two due to the rapid cell membrane permeability.

Diazoacetate polymerization has attracted considerable research attention because it is an effective approach for fabricating carbon–carbon (C–C) main chain polymers. However, diazoacetate polymerization based on inexpensive catalysts has been a long-standing challenge. Herein, we report a Ni(II) catalyst that can promote the living polymerization of various diazoacetates, yielding well-defined C–C main chain polymers, polycarbenes, with a predictable molecular weight (Mn) and low dispersity (Mw/Mn). Moreover, the Ni(II)-catalyzed sequential living polymerization of thiophene and diazoacetate monomers affords interesting π-conjugated poly(3-hexylthiophene)-block-polycarbene copolymers in high yields with a controlled Mn, variable compositions, and low Mw/Mn, although the structure and polymerization mechanism of the two monomers differ. Using this strategy, amphiphilic block copolymers comprising hydrophobic poly(3-hexylthiophene) and hydrophilic polycarbene blocks are facilely prepared, which were self-assembled into well-defined supramolecular architectures with tunable photoluminescence.