Atom transfer radical polymerization (ATRP) of oligo(ethylene oxide) monomethyl ether methacrylate (OEOMA ) in water is enabled using CuBr with tris(2-pyridylmethyl)amine (TPMA) as a ligand under blue or green-light irradiation without requiring any additional reagent, such as a photo-reductant, or the need for prior deoxygenation. Polymers with low dispersity (Đ = 1.18-1.25) are synthesized at high conversion (>95%) using TPMA from three different suppliers, while no polymerization occurred with TPMA is synthesized and purified in the laboratory. Based on spectroscopic studies, it is proposed that TPMA impurities (i.e., imine and nitrone dipyridine), which absorb blue and green light, can act as photosensitive co-catalyst(s) in a light region where neither pure TPMA nor [(TPMA)CuBr] absorbs light.
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http://dx.doi.org/10.1002/marc.202200855 | DOI Listing |
Nanoscale
January 2025
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Dalton Trans
December 2024
Department of Chemistry, Faculty of Science, Karadeniz Technical University, 61080 Trabzon, Turkey.
A series of new cationic first-row transition metal complexes of [Mn(sac)(HO)(tpma)](sac)·HO (Mn), [(μ-O){FeCl(tpma)}](sac)·3HO (Fe), [Co(sac)(HO)(tpma)](sac)·HO (Co), [Ni(HO)(tpma)](sac)·2HO (Ni), [Cu(sac)(tpma)](sac) (Cu) and [Zn(sac)(HO)(tpma)](sac) (Zn), where sac = saccharinate and tpma = tris(2-pyridylmethyl)amine, were synthesized and structurally characterized by elemental analysis, UV-Vis, IR, ESI-MS, NMR, X-ray diffraction and conductivity measurements. The cytotoxic activity of the metal complexes was evaluated against lung carcinoma (A549), breast adenocarcinoma (MCF7), colon (HT29), and normal BEAS-2B cell lines. Mn and Fe displayed potent cytotoxic activity in all cell lines with IC values between 1.
View Article and Find Full Text PDFACS Macro Lett
October 2024
Chair of Macromolecular Materials and Fiber Chemistry, Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
Inorg Chem
September 2024
Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy.
Tris(2-pyridylmethyl)amine () and tris(2-phenolmethyl)amine () metal complexes have been extensively used for catalysis and molecular recognition applications. In particular, due to their ability to form stereodynamic complexes through the helical arrangement of the ligand around the metal in a propeller shape, chiroptical sensing has been extensively investigated. In particular, the capability of the analyte, usually a Lewis base, to bind the metal complex has been the predominant recognition motif.
View Article and Find Full Text PDFDalton Trans
August 2024
Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, 35131 Padova, Italy.
Tris-(2-pyridylmethyl)amines (TPA or TPMA) are polipyrydine-based ligands extensively used in catalysis and supramolecular chemistry due their capability to form stable tetradentate complexes with a large variety of metals. The unsubstituted ligand, which is also commercially available, can be synthesised by consecutive alkylation of a picoline or by reductive amination of a pyridine aldehyde. In this article, we report a novel synthetic method which opens to the post-functionalisation of these ligands in the benzylic position.
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