Controlling the self-assembly morphology of π-conjugated block copolymer is great interesting. Herein, amphiphilic poly(3-hexylthiophene)-block-poly(phenyl isocyanide)s (P3HT-b-PPI) copolymers composed P3HT and optically active helical PPI segments were readily prepared. Taking advantage crystallizable nature chirality segment, crystallization-driven asymmetric (CDASA) lead to formation single-handed nanofibers with controlled length, narrow dispersity, well-defined helicity. During process,...

ConspectusInspired by the perfect helical structures and resulting exquisite functions of biomacromolecules, polymers have attracted increasing attention in recent years. Polyisocyanide is well known for its distinctive rodlike structure various applications chiral recognition, enantiomer separation, circularly polarized luminescence, liquid crystallization, other fields. Although methods catalysts isocyanide polymerization been reported, precise synthesis polyisocyanides with controlled...

A family of air-stable (phenylbuta-1,3-diynyl)palladium(II) complexes were designed and prepared in a facile synthetic procedure. Their structures characterized by (1)H (13)C NMR, MS, X-ray analysis. These Pd revealed to efficiently initiate the polymerization phenyl isocyanides living/controlled chain growth manner, which led formation poly(phenyl isocyanide)s with controlled molecular weights narrow weight distributions. NMR analysis indicated isolated isocyanide) was high...

In this work, air-stable palladium(II) catalysts bearing bidentate phosphine ligands were designed and prepared, which could initiate fast living polymerizations of various diazoacetate monomers under mild conditions. The polymerization afforded the desired polymers in high yields with controlled molecular weights (Mns) narrow weight distributions (Mw/Mns). Mns isolated linearly correlated to initial feed ratios monomer catalyst, confirming living/controlled manner polymerizations. Mn also...

Porous materials have recently attracted much attention owing to their fascinating structures and broad applications. Moreover, exploring novel porous polymers affording the efficient capture of iodine is significant interest. In contrast reported fabricated with small molecular blocks, we herein report preparation polymer frameworks using rigid polyisocyanides as building blocks. First, tetrahedral four-arm star predictable weight low dispersity were synthesized; chain-ends polyisocyanide...

Programming the organization of semiconducting polymers to form well-defined nanoarchitectures is desirable for fabricating functional materials. In this work, copolymers, poly(cholesterol allene)-b-poly(3-hexylthiophene) (PCA-b-P3HT) containing helical PCA and poly(alkoxy (PAA-b-P3HT) achiral PAA segments, were prepared. Crystallization P3HT helicity drove PCA-b-P3HT self-assemble into spherical nanoparticles that gradually transformed one-handed nanofibers. The chirality was transferred...

Cyclic polymers attract attention because of their endless structure and unique properties, which differ from the linear analogs. However, synthesis cyclic is difficult prohibits functions applications. In this study, we reported chiral PdII -catalysts that initiate a living ring-expansion polymerization isocyanides, yielding single-handed cyclic-helical poly(phenyl isocyanide), with predictable molecular weight (Mn ) low dispersity (Mw /Mn ), in good yield. Using method, bottlebrush were...

The significant research progress (from 2011 to 2021) in artificial helical polymers, such as polyacetylenes, polyisocyanides, polycarbenes, etc. , the fields of asymmetric organocatalysis is described.

In this contribution, we report on the facile synthesis of hybrid silica nanoparticles grafted with helical poly(phenyl isocyanide)s via both "grafting from" and to" strategies. First, triethoxysilanyl functionalized alkyne–Pd(II) initiator was anchored onto surface bare through silanization coupling reaction. Polymerization phenyl isocyanide using Pd(II)–anchored lead to formation isocyanide)s. The surface-initiated polymerization revealed proceed in a living/controlled chain-growth manner,...

A left-handed helical poly(phenyl isocyanide) bearing a norbornene unit and Pd(II) complex on each terminus was prepared. The core cross-linked with bisnorbornene linker via ring-opening metathesis polymerization (ROMP), yielding star polymer carrying arms decorated units at the exterior. optical activities of were maintained after cross-linking reaction. surface chain extended new phenyl isocyanide three hydrophilic triethylene glycol monomethyl chains, which afforded an amphiphilic block...

A novel enantiopure phenyl isocyanide (1) carrying l-proline derivative was designed and synthesized. Living polymerization of 1 using a alkyne-Pd(II) catalyst affording series helical poly-1ms with controlled molecular weights (Mns) narrow weight distributions (Mw/Mns) bearing ester as the pendants. Removed protecting groups on pendants lead to formation poly-1m-A. Very interestingly, left-handed backbone poly-1m reversed right-handed helix in poly-1m-A revealed by circular dichroism (CD)...

Abstract Inspired by the exquisite helices in Nature, fabrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis single left‐ and right‐handed polyisocyanides through living polymerization achiral monomers using chiral palladium catalysts under helix‐sense‐selective manner. Mechanism study revealed that yielded opposite showed different activity chain end. The helix unfavored was self‐terminated, while one favored...

Abstract Self‐sorting plays a crucial role in living systems such as the selective assembly of DNA and specific folding proteins. However, self‐sorting artificial helical polymers biomacromolecules has rarely been achieved. In this work, single‐handed poly(phenyl isocyanide)s bearing pyrene (Py) naphthalene (Np) probes were prepared, which exhibited interesting properties driven by both helicity molecular weight ( M n ) solution, solid state, gel, on gel surface well. The with same helix...

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, series well-defined poly(l-lactic acid) (PLLA) poly(d-lactic (PDLA) bearing polymerizable phenyl isocyanide chain ends were prepared. Polymerization the terminal these macromonomers by an alkyne-palladium(II) catalyst yielded PLLA or PDLA atom. The grafted directly packed together without separating from other atoms....

In this work, we reported a strategy to synthesize well-defined bottlebrush polymers. Diazoacetate macromonomers of polystyrene (1-PSn) with controlled molecular weights were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization. The diazo can tolerate the RAFT polymerization conditions and remained on end yielded PS macromonomer. terminal groups macromonomer polymerized by allyl PdCl/L catalyst afford polymers ((1-PSn)ms) carrying side each backbone atom....

Aggregation-induced emission (AIE) active tetraphenylethene (TPE) functionalized phenyl isocyanide (PI) derivatives, such as TPE pendent PI monomers (TPE-NC) and TPE-based Pd(II) catalysts (TPE-Cat. a TPE-Cat. b) were synthesized. The corresponding linear (poly(TPE-NC)n) four-armed (TPE-[poly(TPE-NC)m]4) conjugated polymers subsequently prepared through the living polymerization of TPE-NC with or b in THF, respectively. All them have good solubility common organic solvents, THF CHCl3,...

Two allene derivatives, l- and d-N-(1-(octylamino)-1-oxopropan-2-yl)-4-(propa-1,2-dien-1-yloxy)benzamide (l-1 d-1), bearing chiral amide pendants were designed synthesized. Living polymerizations of l-1 d-1 with allylnickel complex as a catalyst afforded poly-l-1m poly-d-1m controlled molecular weights narrow weight distributions. These polymers found to possess stable helical conformation preferred handedness in aprotic solvents on the basis their circular dichroism (CD) spectra specific...

A class of amphiphilic rod–rod diblock copolymers composed hydrophilic π-conjugated poly(3-triethylene glycol thiophene) (P3(TEG)T) and hydrophobic rigid-rod-like poly(phenyl isocyanide) (PPI) was synthesized in one pot via mechanistically distinct, sequential block copolymerization with Ni(dppp)Cl2 as a single catalyst. The P3(TEG)T homopolymer self-assembled into well-defined nanoparticles THF methanol different dimensions exhibited orange-light emission red-light methanol. Interestingly,...

Facile synthesis of hybrid block copolymers containing two segments that cannot be synthesized under the same polymerization mechanism still remains a great challenge in field polymer synthesis. Here we report on one-pot conjugated poly(phenyleneethylene) (PPE) and stereoregular poly(phenyl isocyanide) (PPI) using palladium(II) complex as single catalyst. Although blocks were polymerized via distinct mechanism, copolymerization revealed to proceed living/controlled chain-growth manner,...

A family of coil–rod–coil ABA triblock copolymers containing poly(3-hexylthiophene) (P3HT) and poly(hexadecyloxyallene) (PHA) were facilely synthesized in one-pot via three sequential living polymerizations hexadecyloxyallene, 2-bromo-3-hexyl-5-chloromagnesiothiophene, hexadecyloxyallene using the π-allylnickel complex as a single catalyst. Although different monomers polymerized under distinct polymerization mechanisms, block copolymerization revealed to proceed living/controlled...

An air-stable phenylethynyl palladium(<sc>ii</sc>) complex was unexpectedly found to initiate the living polymerization of phenyl isocyanide.

We report a new method for facile synthesis of block and star copolymers composed helical poly(phenyl isocyanide) polyacrylate segments via combination Pd(II)-initiated isocyanide polymerization reversible addition–fragmentation chain transfer (RAFT) controlled radical polymerization. First, an alkyne–Pd(II) complex containing benzyl trithiocarbonate substituent was designed synthesized. The Pd(II) moiety the can catalyzed living phenyl isocyanides, while unit be used as agent RAFT Upon two...

Polymerization of phenyl isocyanide using achiral Pd(II) initiator with the presence chiral l- or d-lactide (l-LA d-LA) as additive was found to proceed in helix-sense-selective manner. The polymerization isocyanide, 4-isocyanobenzoyl-2-aminoisobutyric acid decyl ester (1) by this method produced optically active helical poly-1m(L), whose chirality solely come from conformation without containing any other atoms. added LA can be facilely recovered and reused polymerizations significantly...