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Polymers 2016, 8(2), 26; doi:10.3390/polym8020026

Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes

1
CNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France
2
Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris, France
*
Author to whom correspondence should be addressed.
Academic Editor: Nicolay V. Tsarevsky
Received: 31 December 2015 / Revised: 14 January 2016 / Accepted: 19 January 2016 / Published: 22 January 2016
(This article belongs to the Special Issue Controlled/Living Radical Polymerization)
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Abstract

A well-defined amphiphilic core-shell polymer functionalized with bis(p-methoxy-phenylphosphino)phenylphosphine (BMOPPP) in the nanogel (NG) core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG (TPP = triphenylphosphine) and core cross-linked micelles (L@CCM; L = TPP, BMOPPP) having a slightly different architecture were loaded with [Rh(acac)(CO)2] or [RhCl(COD)]2 to yield [Rh(acac)(CO)(L@Pol)] or [RhCl(COD)(L@Pol)] (Pol = CCM, NG). The interparticle metal migration from [Rh(acac)(CO)(TPP@NG)] to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture (CCM vs. NG). The cross-exchange using [Rh(acac)(CO)(BMOPPP@Pol)] and [RhCl(COD)(TPP@Pol)] (Pol = CCM or NG) as reagents at natural pH is also rapid (ca. 1 h), although slower than the equivalent homogeneous reaction on the molecular species (<5 min). On the other hand, the subsequent rearrangement of [Rh(acac)(CO)(TPP@Pol)] and [RhCl(COD)(TPP@Pol)] within the TPP@Pol core and of [Rh(acac)(CO)(BMOPPP@Pol)] and [RhCl(COD)(BMOPPP@Pol)] within the BMOPPP@Pol core, leading respectively to [RhCl(CO)(TPP@Pol)2] and [RhCl(CO)(BMOPPP@Pol)2], is much more rapid (<30 min) than on the corresponding homogeneous process with the molecular species (>24 h). View Full-Text
Keywords: core cross-linked micelles; interparticle molecular migration; phosphine-functionalized polymers; polymer latex; RAFT polymerization; rhodium complexes core cross-linked micelles; interparticle molecular migration; phosphine-functionalized polymers; polymer latex; RAFT polymerization; rhodium complexes
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Chen, S.; Manoury, E.; Gayet, F.; Poli, R. Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes. Polymers 2016, 8, 26.

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