Pyridine attacks : Nucleophilic addition of pyridine derivatives to a doubly linked corrole, which is a stable singlet biradical species, occurs at the bay area with high regioselectivity to provide zwitterionic dimers (see picture; Ar=C6F5). Charge transfer between the anionic corrole and the pyridinium groups induces effective fluorescence quenching of the corrole dimer, which can be utilized for selective fluoride ion recognition.
Divide and conquer : Polymer nanoparticles with phase‐separation structures prepared with block copolymers and homopolymer blends were used to fabricate unique suprapolymer structures by cross‐linking one polymer moiety and dissolving the other (see scheme; PI=polyisoprene, PSt=polystyrene).
Post-synthesis modification of polymers streamlines the synthesis of functionalized polymers, but is often incomplete due to the negative polymer effects. Developing efficient polymer reactions in artificial systems thus represents a long-standing objective in the fields of polymer and material science. Here, we show unprecedented macrocycle-metal-complex-catalyzed systems for efficient polymer reaction that result in 100 % transformation of the main chain functional groups presumably via a processive mode reaction. The complete polymer reactions were confirmed in not only intramolecular reaction (hydroamination) but also intermolecular reaction (hydrosilylation) by using Pd- and Pt-macrocycle-catalyzed systems. The most fascinating feature of the both reactions is that higher-molecular-weight polymers reach completion faster. Various studies suggested that the reactions occur in the catalyst cavity via the formation of a supramolecular complex between the macrocycle catalyst and polymer substrate like pseudorotaxane, which should be of characteristic of the efficient polymer reactions progressing in a processive mode. 相似文献
