Visible Chromophore Phosphines as Functional Elements of Luminescent Metallopolymers

Abstract

A general modular route to fluorophore-linked diphosphines from (4-iodophenyl)P(O)Ph(2) is described. The preparation of chromophoric diphosphine (LHP1) proceeded readily using this route. LHP1 was employed to prepare luminescent metallopolymers of platinum (P1) and palladium (P2) exhibiting modest degrees of polymerization (13-14) and extents of polymerization ( approximately 97%). P1 and P2 appear to be the first metallopolymers polymerized via a visible-absorbing/emitting diphosphine. The photophysical properties of these novel materials are discussed.

Convenient synthetic route to tetraarylphosphonium polyelectrolytes via palladium‐catalyzed P–C coupling of aryl triflates and diphenylphosphine

“…In 2015, we reported the first transition metal‐catalyzed P–C bond formation route to TPELs via coupling of bis(triarylphosphine) and aryl dihalide monomers . The scope and potential for commercialization of this methodology is limited by the expensive, multistep methodologies required to prepare the requisite bis(triarylphosphine) monomers . We recently reported a significantly simplified route to TPELs via direct Ni‐ or Pd‐catalyzed P–C coupling polymerization of commercial aryl dihalides and diphenylphosphine [Scheme (C)] .…”

A new route to phosphonium polymer network solids via cyclotrimerization

“…Compared with traditional organic frameworks, ionic hypercrosslinked polymers, specifically those involving ionic liquids as monomers, have attracted growing attention. These materials can possess good thermal and chemical stability, properties that can be tuned upon simple counterion exchange, and which can readily form layer‐by‐layer self‐assembled films with other ionic polymers . For example, Yang et al reported an alkaline anion exchange membrane R1 (Scheme ) comprised of copolymerized imidazolium‐functionalized ionic liquids with styrene and acrylonitrile.…”

“…These materials can possess good thermal and chemical stability, properties that can be tuned upon simple counterion exchange, and which can readily form layer-bylayer self-assembled films with other ionic polymers. [11][12][13][14][15][16][17][18][19][20] For example, Yang et al reported an alkaline anion exchange membrane R1 (Scheme 1) comprised of copolymerized imidazolium-functionalized ionic liquids with styrene and acrylonitrile. Membranes of R1 demonstrated good hydroxide ion conductivity and mechanical properties suitable for use in alkaline fuel cells.…”

Phosphonium polyelectrolytes: influence of diphosphine spacer on layer‐by‐layer assembly with anionic conjugated polymers

“…Examples of phosphorus‐containing polymers with promise for more recently emerging technologies, such as semiconducting π‐conjugated polymers incorporating low‐coordinate phosphorus centers, have also been reported . Phosphines are among the best‐studied ligands for coordination chemistry and catalysis, and have thus naturally drawn attention as elements of coordination polymers as well …”

“…ammonium, imidazolium, pyridinium etc.). 18 -32 The preparation of ionic polymers that feature other less-common charge-bearing moieties, including those with heavier main group elements such as phosphorus, is of interest to access an expanded set of properties. Each unique charge-bearing unit will have a different polarizability, hydrophobicity/hydrophilicity etc.…”