Multifunctional Block Copolymer: Where Polymetallic and Polyelectrolyte Blocks Meet

Abstract

Sequential reversible addition−fragmentation transfer (RAFT) polymerization of a mixed sandwich cobaltocene monomer (η 5 -cyclopentadienyl-cobalt-η 4 -cyclobutadiene (CpCoCb)) and a phosphonium salt functionalized styrene monomer resulted in the first example of a unique multifunctional block copolymer consisting of a metallopolymer block and a polyelectrolyte block. The polyelectrolyte block was decorated with a gold anion (AuCl 4 − ) via salt metathesis, resulting in a heterobimetallic block copolymer with distinct gold and cobalt sections. Solution self-assembly behavior of this unique metallopolymer-b-polyelectrolyte copolymer before and after salt metathesis was studied. Heterobimetallic micelles with a gold containing core and a cobalt-containing corona were obtained, and then the core was reduced to form gold nanoparticles (AuNPs). Studies on the solid-state self-assembly of this unique block copolymer showed that it phase separated into hexagonally packed cylinders. Salt metathesis of the phase-separated block copolymers was utilized as the first example of a nonstandard selective staining method to exclusively stain the polyelectrolyte domains with the AuCl 4 − anion. Staining the metallopolymer domain by RuO 4 provided the complementary pattern. Pyrolysis of the self-assembled block copolymers resulted in magnetic cobalt-phosphate nanoparticles with 17% char yield.

Intercation spacing and side chain effects on phosphonium polymers: Thermal, supramolecular, and bactericidal properties

“…The molecular weights and degrees of polymerization are summarized in Table . Because these ionomers are too polar to efficiently pass through a gel permeation chromatography column, the degrees of polymerization were determined from NMR end‐group analysis . A slight excess of phosphine monomer was employed to ensure the identity of the end group.…”

Diphenylphosphino Styrene‐Containing Homopolymers: Influence of Alkylation and Mobile Anions on Physical Properties

“…These efforts, unfortunately, reveal a major limitation in the selection of phosphorus‐containing monomers, extending to a small library of vinylbenzyl‐, acrylate‐, and methacrylate‐polymerizable units . A broader selection of phosphorus‐containing monomers will enable the synthesis of low‐viscosity, high‐conductivity phosphonium‐containing macromolecules, inspiring future directions in polymer synthesis and architectural designs …”

Living ROMP Synthesis and Redox Properties of Diblock Ferrocene/Cobalticenium Copolymers

“…According to the kinetic study (see the Supporting Information), the polymerization was completed in 30 min with 100% monomer conversion. Even faster polymerization has been observed with a more soluble monomer . Two molar feed ratios of monomer to catalyst (25:1 and 50:1) were used to prepare cobalticenium‐containing polymers 5 with different molecular weights (MWs), named respectively, 5 (25) and 5 (50).…”

“…Macromolecules containing metals are attracting a great interest due to their multiple materials properties . Recent research has focused on block copolymers, and in particular on diblock copolymers containing metal‐containing groups such as ferrocenyl (Fc) or cobalticenium in their side chains . These copolymers were synthesized using various polymerization methods and showed materials properties of polyelectrolytes, micelles, and magnetic materials.…”