title: Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.
abstract: Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface.
authors.affiliation: CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, 31077, Toulouse, France.
authors.forename: Si
authors.initials: S
authors.lastname: Chen
authors.affiliation: CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, 31077, Toulouse, France.
authors.forename: Florence
authors.initials: F
authors.lastname: Gayet
authors.affiliation: CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, 31077, Toulouse, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Manoury
authors.affiliation: CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, 31077, Toulouse, France.
authors.forename: Ahmad
authors.initials: A
authors.lastname: Joumaa
authors.affiliation: CNRS, UMR 5265, Chemistry, Catalysis, Polymers and Processes (C2P2), Team LCPP, Université de Lyon, Univ. Lyon 1, CPE Lyon, 69616, Villeurbanne, France.
authors.forename: Muriel
authors.initials: M
authors.lastname: Lansalot
authors.affiliation: CNRS, UMR 5265, Chemistry, Catalysis, Polymers and Processes (C2P2), Team LCPP, Université de Lyon, Univ. Lyon 1, CPE Lyon, 69616, Villeurbanne, France.
authors.forename: Franck
authors.initials: F
authors.lastname: D'Agosto
authors.affiliation: CNRS, Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, 31077, Toulouse, France. rinaldo.poli@lcc-toulouse.fr.|Institut Universitaire de France, 103, bd Saint-Michel, 75005, Paris, France. rinaldo.poli@lcc-toulouse.fr.
authors.forename: Rinaldo
authors.identifier: http://orcid.org/0000-0002-5220-2515
authors.initials: R
authors.lastname: Poli
keywords: P ligands; nanostructures; polymer micelles; rhodium; surfaces and interfaces