Andrew J. Inglis

Ultrafast click conjugation of macromolecular building blocks at ambient temperature.

Block copolymers in seconds: Catalyst-free, ambient-temperature click conjugation of individual polymer strands becomes possible using novel ATRP-derived cyclopentadienyl-capped polymers in an extremely rapid hetero-Diels-Alder cycloaddition with macromolecules equipped with electron-deficient dithioester end groups prepared by the RAFT process.

Post-Functionalization of Polymers via Orthogonal Ligation Chemistry†

The establishment of advanced living/controlled polymerization protocols allows for engineering synthetic polymers in a precise fashion. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side-chain functionalization. The review highlights the current status of selected post-functionalization techniques of polymers via orthogonal ligation chemistries, major characteristics of the specific transformation chemistry, as well as the characterization of the products.

Ultra Rapid Approaches to Mild Macromolecular Conjugation

In light of the increasing demand for ultra rapid and mild conjugation chemistries for use in macromolecular chemistry, the present Feature Article provides a critical overview of the very latest developments in this field. The principal aim, therefore, is the provision of a quick selection guide to aid in the formulation of a design strategy for novel functional materials and to provide recommendations for future developments in the chemistries discussed.

Ultra‐Fast RAFT‐HDA Click Conjugation: An Efficient Route to High Molecular Weight Block Copolymers

The use of the reversible addition fragmentation chain transfer-hetero Diels-Alder (RAFT-HDA) click reaction for the modular construction of block copolymers is extended to the generation of high molecular weight materials. Cyclopentadienyl end-functionalized polystyrene (PS-Cp) prepared via both atom transfer radical polymerization (ATRP) and the RAFT process are conjugated to poly(isobornyl acrylate) (PiBoA) (also prepared via RAFT polymerization) to achieve well-defined block copolymers with molecular weights ranging from 34 000 to over 100 000 g · mol(-1) and with small polydispersities (PDI < 1.2). The conjugation reactions proceeded in a very rapid fashion (less than 10 min in the majority of cases) under ambient conditions of temperature and atmosphere. The present study demonstrates-for the first time-that RAFT-HDA click chemistry can provide access to high molecular weight block copolymers in a simple and straight-forward fashion.

Reversible Diels‐Alder Chemistry as a Modular Polymeric Color Switch

(Figure Presented) A fully reversible polymeric color-switch system based on reversible Diels-Alder chemistry between cyclopentadienyl capped polymers and highly electron deficient dithioesters is described. The detailed reaction progress could be mapped on a molecular level for several complete switching cycles and was underpinned by an ESI-MS study.

Well-defined star shaped polymer-fullerene hybrids via click chemistry†

The use of a hexakisazido macrocyclic methanofullerene proves to be highly efficient in the preparation of 6-arm star polymers via copper(I) catalyzed azide-alkyne cycloaddition.

Thermally reversible Diels-Alder-based polymerization: an experimental and theoretical assessment

A pair of monomers capable of undergoing reversible polymerization—based on reversible Diels–Alder (DA) chemistry—as a function of the applied reaction temperature is presented. Specifically, the reaction of isophorone bis(sorbic carbamate), a difunctional diene, with 1,4-phenylenebis(methylene)bis((diethoxyphosphoryl)methanedithioformate), a difunctional dithioester, was studied in detail. Various factors, including the monomer concentration, the type of solvent, and the presence of a Lewis acid, that influence this step-growth polymerization were evaluated. The solvent type was found to have a significant effect on the DA reaction rate. Under the optimized conditions, which are 1.8 g mol−1 of each monomer in acetonitrile with 1.1 equivalents of zinc chloride at 50 °C for 4 h, a polymer with a peak molecular weight of 9600 g mol−1 (relative to poly(styrene) standards) was obtained. The resulting polymer was employed to investigate the correlation between time, temperature, and percentage of debonded monomers achieved during the retro DA (rDA) reaction. In addition, theoretical predictions of the rDA temperature were obtained via ab initio quantum chemical calculations. The monomeric diene and dienophile system was employed for the calculations of the equilibrium constants at various rDA reaction temperatures to correlate the percentage of bonded molecules with the applied temperature. It was calculated that 60% of the polymer becomes debonded at a temperature (Tqc) of around 220 °C, a result that agrees well with that obtained experimentally (Texp = 219 °C).