This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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Living radical polymerization by the RAFT process

This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Living Radical Polymerization by the RAFT Process - A Second Update

Tetrathiafulvalenes, oligoacenenes, and their buckminsterfullerene derivatives: the brick and mortar of organic electronics.

Radical addition-fragmentation chemistry in polymer synthesis

Among the living radical polymerization techniques, reversible addition–fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347–5393, 2005

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/pola.20986

Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization

The 3,3′′′,3′′′″-tris(butylsulfanyl)-2,2′:5′,2″:5″,2′′′,5′′′,2′′′′:5′′′′,2′′′″-sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1+. was evidenced by the 1H NMR study in the presence of small quantities of trifluoroacetic acid (TFA). This approach allowed a comparison of the relative broadening of proton signals of 1, induced by the electron exchange process with traces of radical cation 1+., and the hfc (hyperfine coupling) constants obtained from the EPR study and DFT calculations. In the radical cation, all of the heterocyclic sulphur atoms are not significantly involved in the delocalisation of the unpaired electron, whereas the opposite holds for the radical anion. Time-dependent DFT calculations reproduced well the wavelengths of the optical transitions observed in the spectroelectrochemical experiments for all the five oxidation states and support the formation of the dianion 12−.

Radical Ions from 3,3′′′,3′′′″-Tris(butylsulfanyl)-2,2′:5′,2″:5″,2′′′,5′′′,2′′′′:5′′′′,2′′′″-sexithiophene: An Experimental and Theoretical Study of the p- and n-Doped Oligomer

Conformational studies by dynamic NMR. 31. Enantiotopomerization and torsional processes in sp2-carbon diaryl-substituted hindered compounds

Etude des stereomutations d'amines aromatiques symetriques, mettant en jeu les processus de rotation autour de la liaison C−N et d'inversion au niveau de N. Mesure des energies d'activation et des barrieres d'inversion

Conformation studies by dynamic NMR. 37. Monitoring the stereomutations of symmetric amines by a chiral auxiliary agent

Tris(trimethylsilyl)silane as mediator in the radical-based allylation reactions of allyl and 2-functionalized allyl phenyl sulfones

5H-Pyridophenoxazin-5-one (PPH), a new anticancer iminoquinone, is able to inhibit a large number of lymphoblastoid and solid tumor-derived cells at submicromolar concentrations. Molecular modeling...

Dante Macciantelli

Papers

Radical Ions from 3,3′′′,3′′′″-Tris(butylsulfanyl)-2,2′:5′,2″:5″,2′′′,5′′′,2′′′′:5′′′′,2′′′″-sexithiophene: An Experimental and Theoretical Study of the p- and n-Doped Oligomer

Conformational studies by dynamic NMR. 31. Enantiotopomerization and torsional processes in sp2-carbon diaryl-substituted hindered compounds

Conformation studies by dynamic NMR. 37. Monitoring the stereomutations of symmetric amines by a chiral auxiliary agent

Tris(trimethylsilyl)silane as mediator in the radical-based allylation reactions of allyl and 2-functionalized allyl phenyl sulfones

Antitumor agents 4. Characterization of free radicals produced during reduction of the antitumor drug 5H-pyridophenoxazin-5-one: an EPR study.