Rigid-rodlike right (P)- and left (M)-handed helical polyisocyanides (P-poly-L-1 and M-poly-L-1) prepared by the living polymerization of an enantiomerically pure phenyl isocyanide bearing an L-alanine pendant with a long n-decyl chain (L-1) with the mu-ethynediyl Pt-Pd catalyst were found to block copolymerize L-1 and D-1 in a highly enantiomer-selective manner while maintaining narrow molecular weight distributions. The M-poly-L-1 preferentially copolymerized L-1 over the antipode D-1 by a factor of 6.4-7.7, whereas the D-1 was preferentially copolymerized with P-poly-L-1 composed of the same L-1 units, but possessing the opposite helicity by a factor of 4.0. Circular dichroism and high-resolution atomic force microscopy revealed that the enantiomer-selective block copolymerizations proceed in an extremely high helix-sense-selective fashion, and the preformed helical handedness determines the overall helical sense of the polyisocyanides irrespective of the configuration of the monomer units of the initiators during the block copolymerizations. The block copolymers are rigid-rod helical polymers with a narrow molecular weight distribution and exhibit a lyotropic smectic liquid crystalline phase.

Controlling the self‐assembly morphology of π‐conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3‐hexylthiophene)‐block‐poly(phenyl isocyanide)s (P3HT‐b‐PPI) copolymers composed of π‐conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization‐driven asymmetric self‐assembly (CDASA) of the block copolymers lead to the formation of single‐handed helical nanofibers with controlled length, narrow dispersity, and well‐defined helicity. During the self‐assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single‐handed helical assemblies of the block copolymers exhibited interesting white‐light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers.

We herein report the construction of a new heteropore COF which consists of two different kinds of micropores with unprecedented shapes. It exists as hollow microspheres and exhibits an extremely high volatile iodine uptake (up to 481 wt%) by encapsulating iodine in the inner cavities and porous shells of the microspheres.

A family of air-stable (phenylbuta-1,3-diynyl)palladium(II) complexes were designed and prepared in a facile synthetic procedure. Their structures were characterized by (1)H and (13)C NMR, MS, and X-ray analysis. These Pd complexes were revealed to efficiently initiate the polymerization of phenyl isocyanides in a living/controlled chain growth manner, which led to the formation of poly(phenyl isocyanide)s with controlled molecular weights and narrow molecular weight distributions. (13)C NMR analysis indicated the isolated poly(phenyl isocyanide) was of high stereoregularity. The Pd unit at the end of the polymer chain could undergo further copolymerization with phenyl isocyanide monomers to give block copolymers. It was also found that incorporation of an electron-donating group on the phenyl group of the Pd complex could improve the catalytic activities. Furthermore, these Pd complexes were tolerant to most organic solvents and applicable to a wide range of isocyanide monomers including alkyl and phenyl isocyanides and even phenyl isocyanide with bulky substituents at the ortho position and diisocyanide monomers. Therefore, this polymerization system is versatile in the preparation of well-defined polyisocyanides with controlled sequence. Bi- and trifunctional Pd complexes with two and three Pd units incorporated onto the same phenyl ring were designed and synthesized. They were also able to initiate the living polymerization of phenyl isocyanide to afford telechelic linear and star-shaped polyisocyanides with controlled molecular weights and narrow molecular weight distributions.

Conspectus Inspired by the perfect helical structures and the resulting exquisite functions of biomacromolecules, helical polymers have attracted increasing attention in recent years. Polyisocyanide is well known for its distinctive rodlike helical structure and various applications in chiral recognition, enantiomer separation, circularly polarized luminescence, liquid crystallization, and other fields. Although various methods and catalysts for isocyanide polymerization have been reported, the precise synthesis of helical polyisocyanides with controlled molecular weight, low dispersity, and high tacticity remains a formidable challenge. Owing to a limited synthesis strategy, the controlled synthesis of topological polyisocyanides has barely been realized. This Accounts highlights our recent endeavors to explore novel catalysts for the living polymerization of isocyanides. Fortunately, we discovered that alkyne-Pd­(II) catalysts could initiate the living polymerization of isocyanides, resulting in helical polyisocyanides with controlled structures, high tacticity, and tunable compositions. These catalysts are applicable to various isocyanide monomers, including alkyl isocyanides, aryl isocyanides, and diisocyanobenzene derivatives. Incorporating chiral bidentate phosphine ligands onto alkyne-Pd­(II) complexes formed chiral Pd­(II) catalysts, which promoted the asymmetric living polymerization of achiral isocyanide, yielding single left- and right-handed helices with highly optical activities. Using alkyne-Pd­(II) catalysts, various topological polyisocyanides have been facilely prepared, including hybrid block copolymers, bottlebrush polymers, core cross-linked star polymers, and organic/inorganic nanoparticles. For instance, various hybrid block polyisocyanides were easily produced by coupling alkyne-Pd­(II)-catalyzed living isocyanide polymerization with controlled radical polymerization and ring-opening polymerization (ROP). Combining the ring-opening metathesis polymerization (ROMP) of norbornene with Pd­(II)-catalyzed isocyanide polymerization, bottlebrush polyisocyanides and core cross-linked star polymers were easily prepared. Pd­(II)-catalyzed living polymerization of poly­(lactic acid)­s with isocyanide termini resulted in densely grafted bottlebrush polyisocyanides with closely packed side chains. Moreover, the surface-initiated living polymerization of isocyanides produced a family of polyisocyanide-grafted organic/inorganic hybrid nanoparticles using nanoparticles with alkyne-Pd­(II) catalysts anchored on the surfaces. Surprisingly, the nanoparticles and star polymers with helical polyisocyanide arms performed exceptionally well in terms of chiral recognition and resolution. Incorporated organocatalysts such as proline and prolinol units onto the pendants of optically active helical polyisocyanides, a family of polymer-based chiral organocatalysts, were generated, which showed significantly improved stereoselectivity for the asymmetric Aldol reaction and Michael addition and can be easily recycled. Us...

A modular and convenient synthesis of ethynyl end functionalized poly(3-hexylthiophene) in high purity is reported; this material facilitated access to poly(3-hexylthiophene)-block-poly(acrylic acid) which self-assembled into hierarchical structures.

A new high molecular weight aromatic polyimide has been synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2,2'-dimethyl-4,4'-diaminobiphenyl (DMB) in p-chlorophenol at elevated temperature. BPDA-DMB fibers have been spun by a dry-jet wet spinning method. The fibers were elongated and annealed at elevated temperatures above 400 "C to achieve excellent mechanical properties. In seven times drawn fibers, the BPDA-DMB molecule packs into a triclinic unit cell with dimensions of u = 2,10(2) nm, b = 1,523(8) nm, c = 4,12(7) nm, a = 61,2(6) ", / 3 = 50,7(7) O, and y = 78,9(6) with the number of chain repeating units per unit cell (2) is sixteen. After annealing at elevated temperatures, the fibers produce a small modification of the unit cell [a = 2,048(6) nm, b = 1,529(5) nm, c = 4,00(2) nm, a = 62,1(3) ' , /3 = 52,2(3) O and y = 79,6(3) "I. By increasing the draw ratio, both the crystallinity and crystal orientation increase. The BPDA-DMB fibers possess a decomposition temperature of 530 "C in nitrogen and 500°C in air at a 5% weight loss when the heating rate is 10"C/min. After extensive drawing, BPDA-DMB fibers exhibit a tensile strength of 3,3 GPa and a tensile modulus of over 130 GPa.Dynamic mechanical behavior of the fibers show both a (glass transition) and p (sub-glass transition) relaxations above room temperature. The nature of the sub-glass transition behavior is described as a noncooperative motion attributed to the diamine portion of the molecule. The activation energy for this relaxation in as-spun fibers is 109 kJ/mol and increases to 144 kJ/mol by increasing the draw ratio. This p relaxation is found to be crystallinity dependent. The a transition is also suppressed by crystallinity which increases with draw ratio.

Inspired by the exquisite helices in Nature,f abrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis of single left-and right-handed helical polyisocyanides through living polymerization of achiral monomers using chiral palladium catalysts under helix-sense-selective manner.Mechanism study revealed that the yielded helices with opposite handedness showed different activity of the living chain end. The helix with unfavored handedness was selfterminated, while the one with favored handedness showed high activity and could undergo chain propagation to form ah igh molecular weight polymer with maintained singlehanded helicity.