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This communication reports a versatile post-modification reaction of poly(pentafluorostyrene) building blocks in order to design multifunctional graft copolymers by taking advantage of the selective replacement of the para-fluorine groups.

The combinatorial optimization of the reaction conditions of 1,16-bis(2,2‘:6‘,2‘ ‘-terpyridin-4‘-yloxy)hexadecane 1 with RuCl3 under reductive conditions to form supramolecular polymers with a bis-tpy-Ru(II) type connectivity, utilizing gel permeation chromatography as well as UV/vis spectroscopy as screening tools, led to an improved understanding of important polymerization parameters. Moreover, the obtained knowledge could be applied to the designed synthesis of an A-b-B-b-A type supramolecular triblock copolymer utilizing a α-terpyridine-ω-methyl-poly(ethylene glycol) polymer as a chain stopper during the polycondensation-like reaction. The resulting triblock copolymer revealed a composition of approximately 33 repeat units of 1, outlining the value of the applied optimized conditions for its synthesis. Furthermore, it was observed that the synthesized triblock copolymer was able to form micelles in water. Finally, these micelles were investigated by dynamic light scattering, atomic force microscopy, as well as transmission electron microscopy.

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Multicompartment micelles with tunable compartment solubility have been prepared in alcohols from a metallo-supramolecular poly(p-tetrafluoromethylstyrene)-block-poly(tert-butylacrylate)-block-poly(styrene)-[Ru]-poly(ethylene glycol) tetrablock quaterpolymer.

The synthesis of a new difunctional nitroxide initiator combining two orthogonal supramolecular entities is reported; controlled radical polymerization of styrene using this initiator is demonstrated to generate well-defined heterotelechelic polymers in a one-step procedure.

1,1‐Diphenylethylenene (DPE) was copolymerized anionically with styrene to yield well‐defined alternating copolymers, which were terminated by reacting the “living” polymeric carbanion species with 4′‐chloro‐2,2′:6′2″‐terpyridine. DPE containing polymers show improved long‐term service temperatures due to the stiffening of the polymer main chain by the bulky phenyl‐rings. In addition, the functionality provided by the terpyridine group allows the synthesis of attractive materials for various fields of application. The obtained polymers were fully characterized by means of nuclear magnetic resonance, gel permeations chromatography, elemental analysis, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, ultraviolet‐visible spectroscopy, and macromolecular hydrodynamic methods (analytical ultracentrifugation, gel permeation chromatography, intrinsic viscosimetry). In the molar mass range of 2 < M < 25 kg/mol, the scaling relationships between M and hydrodynamic characteristics are obtained. The values of the Kuhn segment length (or persistence length) and hydrodynamic diameters are evaluated and compared with those of linear polystyrene. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3691–3701, 2009

The post-modification of polypentafluorostyrene via the selective substitution of the para- fluorine by amine-functionalized molecules represents a versatile method for the preparation of functional materials. This communication presents the extension of this synthetic approach towards metallosupramolecular materials. First, the incorporation of terpyridines as metallo-supramolecular binding motifs is demonstrated, which enables the formation of a supramolecular crosslinked gel upon the addition of Fe(II) ions. Second, the linkage of phosphorescent iridium(III) complexes is reported yielding a copolymer that combines the excellent photophysical properties of the iridium(III) complex and the good solubility and processability of the polymer.