ROMPI-CDSA: ring-opening metathesis polymerization-induced crystallization-driven self-assembly of metallo-block copolymers

Abstract

Polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) are among the most prevailing methods for block copolymer self-assembly. Taking the merits of scalability of PISA and dimension control of CDSA, we report one-pot synchronous PISA and CDSA via ring-opening metathesis polymerization (ROMP) to prepare nano-objects based on a crystalline poly(ruthenocene) motif. We denote this self-assembly methodology as ROMPI-CDSA to enable a simple, yet robust approach for the preparation of functional nanomaterials. Results and discussionThe synchronous process of PI-CDSA requires the incipient production of a corona-forming block that is carried out under living polymerization in a good solvent medium. The same solvent system becomes non-selective for the second coreforming block as the degree of polymerization (DP) of the second segment proceeds to a threshold that induces crystallization. 22

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

“…[1][2][3][4][5] Even great efforts have been devoted to this area for decades,c ontrol over the morphology and dimensions of supramolecular assemblies is still ag reat challenge,e specially for onedimensional (1D) semiconducting nanostructures. [6][7][8][9] Cylindrical and fiber-liker micelles are among the most attractive 1D morphologies,o wing to their versatile applications,s uch as in nanoelectronic device fabrication, drug delivery. [10][11][12][13] As pioneered by Manners,W innik, and co-workers,a ni nnovative living crystallization-driven self-assembly (CDSA) strategy was developed for fabricating one-and two-dimensional nanostructures from fragmented crystalline block copolymers with controlled lengths and narrow dispersity.…”

Ring-opening polymerization-induced crystallization-driven self-assembly of poly-L-lactide-block-polyethylene glycol block copolymers (ROPI-CDSA)

“…However, PISA can theoretically be extended to all types of living polymerizations and has been demonstrated with living anionic polymerization 35 , ring-opening metathesis (ROMP) of norbornenes 13 , 29 , radical ring-opening copolymerization (rROP) of cyclic ketenes 36 , and ring-opening polymerization (ROP) of N-carboxyanhydrides 37 . PISA has also been combined with CDSA, termed polymerization-induced crystallization-driven self-assembly (PI-CDSA), to generate crystalline self-assemblies in high concentrations (10–25% solids w/w) 15 , 16 , 38 . Currently, PI-CDSA has been demonstrated for sequential living anionic polymerization 15 , 16 , and the ring-opening metathesis of organometallic polymers 38 .…”

“…PISA has also been combined with CDSA, termed polymerization-induced crystallization-driven self-assembly (PI-CDSA), to generate crystalline self-assemblies in high concentrations (10–25% solids w/w) 15 , 16 , 38 . Currently, PI-CDSA has been demonstrated for sequential living anionic polymerization 15 , 16 , and the ring-opening metathesis of organometallic polymers 38 . Polylactones, being semi-crystalline in nature, are excellent candidates for the development of a fully organic PI-CDSA to produce biocompatible, biodegradable BCP materials at high concentration in a scalable process.…”

Rapid formation and real-time observation of micron-sized conjugated nanofibers with tunable lengths and widths in 20 minutes by living crystallization-driven self-assembly

“…To accelerate the self-assembly process and produce nanostructures more efficiently, a one-pot technique named Polymerization-Induced CDSA (PI-CDSA) was developed where CDSA successful occurred during or aer the polymerization. [35][36][37] For the spontaneous formation of the conjugated nanoparticles, we have developed another strategy termed In situ Nanoparticlization of Conjugated Polymers (INCP). [38][39][40][41][42] INCP is a process whereby insoluble conjugated polymers are intentionally introduced as the second block.…”