Combination of methylthio-chemistry with living crystallization-driven self-assembly toward uniformπ-conjugated nanostructures with antibacterial activity,surface tailorability,tunable morphology and dimension

Living crystallization-driven self-assembly(CDSA)provides robust access to uniformπ-conjugated nanostructures(CNSs)from block copolymers(BCPs)containing a crystallineπ-conjugated segment with controlled dimension,morphology and composition,which show appealing applications in biomedicine,photocatalysis and microelectronics.To further expand the application spectrum of these CNSs,the development of facile strategies toward diverse CNSs with varying structures/functionalities is highly desired.Herein,BCPs consisting of oligo(p-phenylene ethynylene)-b-poly(polypropyl-3-methanethiol acrylate)(OPE_(9)-bPMTPA35and OPE_(9)-b-PMTPA_(58);the subscript represents the number of repeat unit of each block)consisting of a crystallineπ-conjugated core-forming OPE_(9)segment and a corona-forming PMTPA block are synthesized.By efficient“click-type”alkylation of methylthio groups,OPE_(9)-b-PMTPA with varying contents of sulfonium unit is obtained.Uniform ribbon-like micelles with different widths and lengths can then be generated in a controlled manner via the self-seeding approach of living CDSA.Additionally,negatively charged polymeric and Ag nanoparticles can be immobilized on sulfonium/methylthio-containing shells by taking advantage of electrostatic attraction and coordination interaction,respectively.Interestingly,the ribbon-like micelles with positively charged shells exhibit antibacterial activity against E.coli.Given the ease of modification of PMTPA-based shell and attractive opto-electronic/photocatalytic properties ofπ-conjugated units,the combination of methylthio-chemistry and living CDSA opens a new avenue to generate multi-functional CNSs for widespread applications from biomedicine to photocatalysis.

Access to Versatile Functionalized Cu(Ⅲ) Complexes Enabled by Direct Transmetalation to Well-Defined Copper(Ⅲ) Fluoride Complex Me_(4)N^(+)[Cu(CF_(3))_(3)F]^(-)

The invention of a well-defined Cu(Ⅲ)fluoride complex Me_(4)N^(+)[Cu(CF_(3))_(3)(F)]^(-)1 enabled to access a versatile of functionalized Cu(Ⅲ)complexes[Me_(4)N]^(+)[Cu(X)(CF_(3))_(3)]^(-)(X=C_(6)F_(5),C_(6)F_(5)C≡C,CN,Cl,N_(3),^(t)BuOO,SCN,OAc,SAr),many of them for the first time.The availability of these complexes allowed us to evaluate the trans-influence order of ligand in Cu(Ⅲ)complexes:Bn>CF_(3)^(-)>C_(6)F_(5)^(-)>N_(3)^(-)>py~CH_(3)^(-)~C_(6)F_(5)C≡C>NO_(2)PhO^(-)~^(t)BuOO^(-)~CH_(3)COO^(-)>F^(-).