Highly-metallized phosphonium polyelectrolytes

Kenaree, Amir Rabiee; Berven, Bradley M.; Ragogna, Paul J.; Gilroy, Joe B.

doi:10.1039/c4cc05296j

Cited by 28 publications

(18 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Tri(ethylferrocene)phosphine 38 and formazan 6b 39 1 H NMR spectra were referenced to residual CHCl 3 ( = 7.27) or C 6 D 5 H ( = 7.16), and 13 C{ 1 H} NMR spectra were referenced to CDCl 3 ( = 77.0) or C 6 D 6 ( = 128.1). 31 P NMR spectra were referenced with respect to H 3 PO 4 ( = 0).…”

Section: General Considerationsmentioning

confidence: 99%

Aluminum Complexes of N₂O₂^3– Formazanate Ligands Supported by Phosphine Oxide Donors

et al. 2017

Self Cite

View full text Add to dashboard Cite

The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an NO formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M cm) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.

show abstract

Section: General Considerationsmentioning

confidence: 99%

Aluminum Complexes of N₂O₂^3– Formazanate Ligands Supported by Phosphine Oxide Donors

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…Polyelectrolytes have been attracting tremendous interest in recent decades due to the growing range of applications available based on their intriguing and unique properties . Phosphonium‐derivatized polyelectrolytes in particular have been investigated for application in diverse applications ranging from their use as antimicrobial agents and biodelivery vectors, to materials and energy applications such as alkaline fuel cell membranes, redox‐active films, ordered optically active materials and optoelectronic devices …”

Section: Introductionmentioning

confidence: 99%

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

Wan

Yang

Smith

2017

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

A series of eight tetraarylphosphonium polyelectrolytes (TPELs) has been successfully synthesized by polymerization of diphenylphosphine and bis(aryl triflate)s. The bis(aryl triflate)s are readily prepared from bisphenols, some of which are commodity feedstocks such as bisphenol A. The polymerization via palladium catalyzed P-C bond formation produces degrees of polymerization up to 65. All polymeric triflates have reasonable thermal stability in the range of 350-450 8C. The stability of the TPELs to alkaline solution is strongly depending on the spacer between adjacent phosphonium sites. Polymers with electron-releasing and bulky substituent para-to the phosphonium site have improved stability while those with electron-withdrawing substituent para-to phosphonium site have decreased alkaline stability due to decomposition via a nucleophilic aromatic substitution pathway. These findings have important ramifications for the design of ionomers for alkaline exchange membrane fuel cells and related electrochemical energy conversion devices.

show abstract

“…Compared with organo-polyelectrolytes, magnetic properties are another unique characteristic for metallo-polyelectrolytes. By carefully selecting metal ions and ligands, magnetic metallo-polyelectrolytes could have tunable magnetic properties 81 – 85 . Owing to the decrease of the crystal field splitting of d-orbital subsets, metal ions in metallo-polyelectrolytes may undergo a spin transition from a low-spin to a high-spin state, resulting in changes of magnetic properties.…”

Section: Functional Materials Via Redox or Electrostatic Interactionsmentioning

confidence: 99%

Metallo-polyelectrolytes as a class of ionic macromolecules for functional materials

et al. 2018

View full text Add to dashboard Cite

The fields of soft polymers and macromolecular sciences have enjoyed a unique combination of metals and organic frameworks in the name of metallopolymers or organometallic polymers. When metallopolymers carry charged groups, they form a class of metal-containing polyelectrolytes or metallo-polyelectrolytes. This review identifies the unique properties and functions of metallo-polyelectrolytes compared with conventional organo-polyelectrolytes, in the hope of shedding light on the formation of functional materials with intriguing applications and potential benefits. It concludes with a critical perspective on the challenges and hurdles for metallo-polyelectrolytes, especially experimental quantitative analysis and theoretical modeling of ionic binding.

show abstract

Highly-metallized phosphonium polyelectrolytes

Abstract: The synthesis, characterization, and pyrolysis of a novel class of highly-metallized, redox-active polyelectrolytes that employ phosphorus as a scaffold for the installation of transition metals is described.

Cited by 28 publications

References 49 publications

Aluminum Complexes of N₂O₂^3– Formazanate Ligands Supported by Phosphine Oxide Donors

Aluminum Complexes of N₂O₂^3– Formazanate Ligands Supported by Phosphine Oxide Donors

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

Metallo-polyelectrolytes as a class of ionic macromolecules for functional materials

Contact Info

Product

Resources

About

Highly-metallized phosphonium polyelectrolytes

Abstract: The synthesis, characterization, and pyrolysis of a novel class of highly-metallized, redox-active polyelectrolytes that employ phosphorus as a scaffold for the installation of transition metals is described.

Cited by 28 publications

References 49 publications

Aluminum Complexes of N2O23– Formazanate Ligands Supported by Phosphine Oxide Donors

Aluminum Complexes of N2O23– Formazanate Ligands Supported by Phosphine Oxide Donors

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

Metallo-polyelectrolytes as a class of ionic macromolecules for functional materials

Contact Info

Product

Resources

About

Aluminum Complexes of N₂O₂^3– Formazanate Ligands Supported by Phosphine Oxide Donors

Aluminum Complexes of N₂O₂^3– Formazanate Ligands Supported by Phosphine Oxide Donors