Reversible Switching between Linear and Ring Polystyrenes Bearing Porphyrin End Groups

A route to macrocyclic polymers based on a new unimolecular ring-closure process has been investigated. It involves the direct end-to-end coupling of an alpha, omega-bis[chloroiron(III) meso-tetraphenylporphyrin] telechelic linear polystyrene synthesized by living polymerization followed by chain-end functionalization. The corresponding macrocyclic polystyrene was obtained readily and selectively by intramolecular condensation of the alpha,omega-bis[chloroiron(III) meso-tetraphenylporphyrin] polymer ends in the presence of a base to yield a diiron(III)-mu-oxobis(porphyrin) dimer as ring-closing unit. Addition of dilute HCl was shown to rapidly reconvert the diiron(III)-mu-oxobis(porphyrin) unit into the initial bis[chloroiron(III) porphyrin], demonstrating the selectivity and complete reversibility of the cydization process. The synthesis and detailed structural characterization of the alpha,omega-homodifunctional precursor and the corresponding macrocyclic polystyrene along with an analysis of the porphyrin dimerization reaction using NMR spectroscopy and size-exclusion chromatography coupled with a diode array detector are presented.