Four new bis(m-phenylene)-32-crown-10-based cryptands with different third bridges were prepared. Their complexes with paraquat derivatives were studied by proton NMR spectroscopy, mass spectrometry, and X-ray analysis. It was found that these cryptands bind paraquat derivatives very strongly. Specifically, a diester cryptand with a pyridyl nitrogen atom located at a site occupied by either water or a PF(6) anion in analogous complexes exhibited the highest association constant K(a) = 5.0 x 10(6) M(-1) in acetone with paraquat, 9000 times greater than the crown ether system. X-ray structures of this and analogous complexes demonstrate that improved complexation with this host is a consequence of preorganization, adequate ring size for occupation by the guest, and the proper location of the pyridyl N-atom for binding to the beta-pyridinium hydrogens of the paraquat guests. This readily accessible cryptand is one of the most powerful hosts reported for paraquats.

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Block copolymers containing polystyrene and polycyclooctene were synthesized with a ring‐opening metathesis polymerization/chain‐transfer approach. Polystyrene, containing appropriately placed olefins, was prepared by anionic polymerization and served as a macromolecular chain‐transfer agent for the ring‐opening metathesis polymerization of cyclooctene. These unsaturated polymers were subsequently converted to the corresponding saturated triblock copolymers with a simple heterogeneous catalytic hydrogenation step. The molecular and morphological characterization of the block copolymers was consistent with the absence of significant branching in the central polycyclooctene and polyethylene blocks [high melting temperatures (114–127 °C) and levels of crystallinity (17–42%)]. A dramatic improvement in both the long‐range order and the mechanical properties of a microphase‐separated, symmetric polystyrene–polycyclooctene–polystyrene block copolymer sample was observed after fractionation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 361–373, 2007

Two sets of styrene‐based semifluorinated block copolymers, one with a perfluoroether pendant group and another with a perfluoroalkyl group, were synthesized by atom transfer radical polymerization. Microphase separation of the block copolymers was established by small‐angle X‐ray scattering and differential scanning calorimetry (DSC). DSC measurements also showed that the perfluoroether‐based polymer had a low glass‐transition temperature (−44 °C). Contact‐angle measurements indicated that the semifluorinated block copolymers had low surface energies (ca. 13 mJ/m2). These materials hold promise as low‐surface‐energy additives or surfactants for supercritical CO2 applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 853–861, 2004

Bis(meta-phenylene)-32-crown-10-based cryptands have been proved to complex diquat much more strongly than bis(meta-phenylene)-32-crown-10 itself; in fact, one containing a pyridyl moiety has one of the highest Ka values yet reported.

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Well-defined polyisoprene three-armed star polymers (PI3) were synthesized through a combination of living anionic polymerization and an efficient coupling process using hexafluoropropylene oxide (HFPO). Anionic polymerization of isoprene followed by termination with HFPO yielded threearmed stars with narrow molecular weight distributions. Under optimized conditions, at least 97% of the chains can be coupled. Molecular characterization of the star polymers (SEC, NMR and IR spectroscopy, and MALDI-TOF mass spectrometry) gave data consistent with the star structure and proposed mechanism of formation. The effects of HFPO concentration and the molecular weight of the arm precursors on the extent of star polymer formation were investigated. End-functionalized polyisoprene stars were also prepared and have potential application as trifunctional precursors to branched block copolymers.