Hypervalent iodine-based dynamic and self-healing network polymers

2019 ◽  
Vol 10 (29) ◽  
pp. 3943-3950 ◽  
Author(s):  
Avichal Vaish ◽  
Nicolay V. Tsarevsky
Keyword(s):  
Ligand Exchange ◽  
Uv Light ◽  
Hypervalent Iodine ◽  
Self Healing ◽  
Linear Polymers ◽  
Exchange Reactions ◽  
Network Polymers ◽  
Radical Coupling

Linear polymers with carboxylate pendant groups participate in ligand-exchange reactions with (diacetoxyiodo)benzene to afford dynamic and self-healing networks, which become set when exposed to UV light or heat due to irreversible radical coupling.

Ultrafast and Reversible Multiblock Formation by the SET-Nitroxide Radical Coupling Reaction

2010 ◽  
Vol 63 (8) ◽  
pp. 1227 ◽  
Author(s):  
Jakov Kulis ◽  
Craig A. Bell ◽  
Aaron S. Micallef ◽  
Michael J. Monteiro
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Elevated Temperatures ◽  
Click Reaction ◽  
Coupling Reaction ◽  
Nitroxide Radical ◽  
Self Healing ◽  
Exchange Reactions ◽  
Radical Coupling ◽  
End Groups

The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50°C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br) with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high-molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.

Employing exchange reactions involving hypervalent iodine compounds for the direct synthesis of azide-containing linear and branched polymers

2014 ◽  
Vol 5 (12) ◽  
pp. 4599-4609 ◽  
Author(s):  
Hongzhang Han ◽  
Nicolay V. Tsarevsky
Keyword(s):  
Ligand Exchange ◽  
Direct Synthesis ◽  
Branched Polymers ◽  
Hypervalent Iodine ◽  
Exchange Reactions ◽  
One Pot ◽  
Iodine Compounds

Azide-containing polymers were prepared by one-pot polymerizations initiated by azide radicals produced by ligand exchange reactions involving hypervalent iodine(iii) compounds.

Voltammetric Studies of Some Novel Fe(III) Complexes with Quadridentate Ligands. The Axial Ligand-Exchange Reactions in DMF and DMSO

1995 ◽  
Vol 60 (7) ◽  
pp. 1140-1157 ◽  
Author(s):  
Ljiljana S. Jovanovic ◽  
Luka J. Bjelica
Keyword(s):  
Oxidation State ◽  
Chemical Reactions ◽  
Ligand Exchange ◽  
Kinetic Data ◽  
Central Atom ◽  
Axial Ligand ◽  
Exchange Reactions ◽  
Ligand Effect ◽  
Condensation Products ◽  
Voltammetric Studies

The electrochemistry of four novel Fe(III) complexes of the type [Fe(L)Cl], involving quadridentate ligands based on the condensation products of benzoylacetone-S-methylisothiosemicarbazone with salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-dichlorosalicylaldehyde or 5-nitrosalicylaldehyde, was studied in DMF and DMSO at a GC electrode. All complexes undergo a two-step one-electron reductions, usually complicated by chemical reactions. In solutions containing Cl-, the ligand-exchange reactions Cl--DMF and Cl--DMSO take place. Stability of the chloride-containing complexes was discussed in terms of the coordinated ligand effect, oxidation state of the central atom and, in particular, of the donor effect of the solvent. Some relevant kinetic data were calculated.

A first-principles study of the atomic layer deposition of ZnO on carboxyl functionalized carbon nanotubes: the role of water molecules

2021 ◽  
Vol 23 (5) ◽  
pp. 3467-3478
Author(s):  
J. I. Paez-Ornelas ◽  
H. N. Fernández-Escamilla ◽  
H. A. Borbón-Nuñez ◽  
H. Tiznado ◽  
Noboru Takeuchi ◽  
...  
Keyword(s):  
First Principles ◽  
Ligand Exchange ◽  
Functional Group ◽  
Atomic Layer ◽  
High Reactivity ◽  
Water Molecules ◽  
Exchange Reactions ◽  
Layer Deposition ◽  
The Right

Atomic description of ALD in systems that combine large surface area and high reactivity is key for selecting the right functional group to enhance the ligand-exchange reactions.

An unusual example ofendo-stereoselectivity in the ligand exchange reactions of rhodium(i)diethylene derivatives withpara-semiquinoid ligands

1996 ◽  
Vol 45 (9) ◽  
pp. 2203-2206 ◽  
Author(s):  
S. V. Sergeev ◽  
V. A. Nikanorov ◽  
S. G. Novikov ◽  
P. V. Petrovskii ◽  
D. V. Zverev
Keyword(s):  
Ligand Exchange ◽  
Exchange Reactions

Post-synthetic functionalization and ligand exchange reactions in gold(i) phenylthiolate-based coordination polymers

2020 ◽  
Vol 44 (41) ◽  
pp. 17970-17975
Author(s):  
Larysa Okhrimenko ◽  
Cynthia Cibaka Ndaya ◽  
Alexandra Fateeva ◽  
Gilles Ledoux ◽  
Aude Demessence
Keyword(s):  
Coordination Polymers ◽  
Ligand Exchange ◽  
Exchange Reactions ◽  
Gold Thiolate ◽  
Post Modification

Post-modification and ligand exchange reactions from 1D or 2D gold thiolate coordination polymers occur through a dissolution–recrystallization pathway.

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