New ROMP Synthesis of Ferrocenyl Dendronized Polymers

Abstract

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method.

Recent advances in metallopolymer-based drug delivery systems

“…2). 34,[82][83][84][85][86][87][88][89][90][91][92][93][94] Coordination polymers (CPs) relate to MPs of Type III containing metal in the main chain, whose special feature is breaking of a polymer chain aer a metal is removed. Because they contain large voids in the crystal structure, they were called porous coordination polymers or metal-organic frameworks (MOFs).…”

Controlled ROMP Synthesis of Ferrocene‐Containing Amphiphilic Dendronized Diblock Copolymers as Redox‐Controlled Polymer Carriers

“…Cis ‐5‐norbornene‐ exo ‐2,3‐dicarboxylic anhydride (95%), ethylenediamine, triethylene glycol monomethyl ether, ethyl vinyl ether (EVE, 99%), 3‐bromopropionyl chloride, oxalyl chloride, ferrocene, glutathione, methyl gallate, and the second generation Grubbs’ metathesis catalyst were purchased from Energy Chemical, and used directly. Grubbs’ 3rd generation catalyst 1 was synthesized following a procedure reported in the literature . All the other chemicals were from commercial sources and used as received.…”

“…This may be taken into account by the difficult synthesis of well‐defined dendronized copolymers with low dispersion and high molecular weight due to the large steric hindrance of bulky dendrons, leading to their far less application in polymeric carriers in comparison with linear polymers . The living and controlled ring‐opening metathesis polymerization (ROMP) technique shows not only excellent reactivity toward bulky monomers under mild reaction conditions but also exceptional functional group tolerance of the Grubbs’ catalyst used in this process, which offers a great advantage to construct perfect DPs by macromonomer strategy …”

Novel Carboxylic Acid Functionalized Dendronized Polymer: A Homogeneous, Reusable Metal Free Acid Catalyst for the Synthesis of Symmetric and Unsymmetric Xanthene Derivatives

“…With increasing generation, the conformation of dendronized polymers change from a random coil to a semiflexible cylinder, and the dendritic structure becomes thicker and stiffer due to large steric repulsion among the side chains [2,3] . The physical properties of these materials can be controlled by altering the polymer main chain composition, the degree of polymerization of the main chain, generation of the grafted side chain, or the charge of the active termini [4–6] . Several research groups have applied dendronized polymers in diverse fields like photonic crystals, [7] drug delivery, [8,9] molecular assemblies, [10] surface coating, [11] non‐aggregating polymer fluorophores, [12] etc.…”

“…[2,3] The physical properties of these materials can be controlled by altering the polymer main chain composition, the degree of polymerization of the main chain, generation of the grafted side chain, or the charge of the active termini. [4][5][6] Several research groups have applied dendronized polymers in diverse fields like photonic crystals, [7] drug delivery, [8,9] molecular assemblies, [10] surface coating, [11] non-aggregating polymer fluorophores, [12] etc. Catalysis is also a relevant application of dendronized polymers due to the unique branching architecture with intramolecular cavities, highly accessible internal surface area, and highly dense multifunctional groups at the periphery.…”