Synthesis and Self-Assembly of Conjugated Polymer Precursors Containing Dichlorocarbonate Groups by Living Ring-Opening Metathesis Polymerization

Abstract

We have used the living ring-opening metathesis polymerization reaction with Cl2(PCy3)2RuCHPh to generate a new class of conjugated polymer precursors containing the reactive group 1,2-dichlorocarbonate in their backbone. These polymers possess narrow molecular weight distributions and are easily processable. We have incorporated the 1,2-dichlorocarbonate monomers into block copolymers and have shown that these systems can self-assemble in selective solvents to generate spherical micellar aggregates (TEM). Mild hydrolytic treatment of these precursor polymers converts them into novel low-band-gap conjugated polymers and block copolymers containing 1,2-diol groups in their backbone.

Precise Tuning of Micelle, Core, and Shell Size by the Composition of Amphiphilic Block Copolymers Derived from ROMP Investigated by DLS and SAXS

“…It has been shown that defined amphiphilic block copolymers can be obtained by ROMP. Several aspects were investigated, such as the formation of stable micelles and nanoparticles, − the use as drug delivering material, , as polymers with special electrooptical and electroactive properties − and for the preparation of inorganic nanoparticles. − For most of the above-mentioned applications, the self-assembly at the nanoscale has to be very precise and homogeneous. This can only be achieved by a very well controlled synthesis of the block copolymers.…”

Ruthenium(II) Dipyridoquinoxaline-Norbornene: Synthesis, Properties, Crystal Structure, and Use as a ROMP Monomer

“…We are currently investigating the properties of the ROMP polymers of 4 in further detail and generating these from enantiomerically pure monomers. In addition, we are studying possible methods for the conversion of the polymer backbone in 5 to a conjugated form, in analogy with our previous studies on a similar system, 11 to create Ru(II)-containing conjugated polymers in a controlled manner.…”

“…Because of their unique photophysical and redox properties, these molecules have been extensively investigated as components of light-harvesting assemblies and photochemically driven molecular devices, as well as photocatalysts and biological probes. − For these applications, binuclear and multinuclear assemblies containing Ru(II) diimine complexes are typically constructed in stepwise syntheses, which can be time-consuming. On the other hand, the ROMP reaction of Ru(II) polypyridyl-containing monomers could result in more straightforward generation of multichromophoric polymers and block copolymers in a living fashion, with controlled molecular weights and narrow molecular weight distributions. , A number of polymeric systems containing Ru(II) diimines have been generated . Free-radical polymerization 12a-d and, more recently, anionic polymerization 12e-i have been used to synthesize precursors that were converted to Ru(bpy) 3 2+ -containing homopolymers.…”

“…On the other hand, the ROMP reaction of Ru(II) polypyridylcontaining monomers could result in more straightforward generation of multichromophoric polymers and block copolymers in a living fashion, with controlled molecular weights and narrow molecular weight distributions. 1,11 A number of polymeric systems containing Ru(II) diimines have been generated. 12 Free-radical polymerization 12a-d and, more recently, anionic polymerization 12e-i have been used to synthesize precursors that were converted to Ru(bpy) 3 2+containing homopolymers.…”

The chemistry of the carbon–transition metal double and triple bond: annual survey covering the year 2002

“…16) [139]; (7) norbornenes connected to pincer-ligated phenylpalladium(II) derivatives (e.g. 17) [140,141]; (8) norbornenes fused to the N-hydroxysuccinimide ring system [142]; (9) norbornenes and oxanorbornenes of general structure 18 [143]; (10) norbornenecarboxylate esters of complex fluorinated benzyl alcohol derivatives [144]; (11) polyethylene glycol-bound norbornenes [145]; (12) adenine-containing norbornene derivatives [146]; (13) norbornene derivatives featuring a thymidine ring associated with a 1,6-diamidopyridine derivative (19) [147]; (14) bicyclo[3.2.0]hept-6-ene [148]; (15) norbornene-fused succinimides [149]; (16) norbornenes attached to oligothiophene units (e.g. 20) [150]; (17) 3,5-siloxane-bridged cyclopentenes (e.g.…”