TY - JOUR
T1 - Pd-complex driven formation of single-chain nanoparticles
AU - Willenbacher, Johannes
AU - Altintas, Ozcan
AU - Trouillet, Vanessa
AU - Knöfel, Nicolai
AU - Monteiro, Michael J.
AU - Roesky, Peter W.
AU - Barner-Kowollik, Christopher
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2015.
PY - 2015/6/28
Y1 - 2015/6/28
N2 - We report the facile synthesis of well-defined palladium(ii) cross-linked single-chain nanoparticles (Pd-SCNPs) using the 'repeating unit approach'. The linear precursor polymer (Mn ≈ 10200 g mol-1, ≈ 1.17) was synthesized via nitroxide mediated statistical copolymerization of styrene and 4-(chloromethyl)styrene (CMS) followed by a post-polymerization modification of the resulting copolymer to covalently attach the triarylphosphine ligand moieties. The ligand content along the lateral polymer chain was 12%. Intramolecular crosslinking was performed in diluted solution with a suitable precursor complex (Pd[1,5-cyclooctadiene]Cl2) to afford the well-defined Pd-SCNPs, which feature a hydrodynamic diameter of Dh = 5.4 nm. The palladium(ii) containing single-chain nanoparticles were characterized in-depth using 1H NMR spectroscopy, 31P{1H} NMR spectroscopy, dynamic light scattering (DLS), size exclusion chromatography (SEC), 1H spin-spin relaxation time (T2) analysis, X-ray photoelectron spectroscopy (XPS), and log-normal distribution (LND) simulations. Finally, the applicability of the Pd-SCNPs as catalyst in the Sonogashira coupling was exemplified.
AB - We report the facile synthesis of well-defined palladium(ii) cross-linked single-chain nanoparticles (Pd-SCNPs) using the 'repeating unit approach'. The linear precursor polymer (Mn ≈ 10200 g mol-1, ≈ 1.17) was synthesized via nitroxide mediated statistical copolymerization of styrene and 4-(chloromethyl)styrene (CMS) followed by a post-polymerization modification of the resulting copolymer to covalently attach the triarylphosphine ligand moieties. The ligand content along the lateral polymer chain was 12%. Intramolecular crosslinking was performed in diluted solution with a suitable precursor complex (Pd[1,5-cyclooctadiene]Cl2) to afford the well-defined Pd-SCNPs, which feature a hydrodynamic diameter of Dh = 5.4 nm. The palladium(ii) containing single-chain nanoparticles were characterized in-depth using 1H NMR spectroscopy, 31P{1H} NMR spectroscopy, dynamic light scattering (DLS), size exclusion chromatography (SEC), 1H spin-spin relaxation time (T2) analysis, X-ray photoelectron spectroscopy (XPS), and log-normal distribution (LND) simulations. Finally, the applicability of the Pd-SCNPs as catalyst in the Sonogashira coupling was exemplified.
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U2 - 10.1039/c5py00389j
DO - 10.1039/c5py00389j
M3 - Article
AN - SCOPUS:84931034400
SN - 1759-9954
VL - 6
SP - 4358
EP - 4365
JO - Polymer Chemistry
JF - Polymer Chemistry
IS - 24
ER -