Electron-Donating Properties of p-Phenylene Phosphine Imides:  An Electrochemical and Spectroscopic Investigation

Abstract

[reaction: see text] Electronic properties of phosphine imide based organic electron donors have been investigated. N,N'-p-Phenylenebis(triphenyl)phosphine imide (Ph(3)P=NC(6)H(4)N=PPh(3), 1) has two reversible single-electron oxidations (0.04 and 0.53 V vs SCE). Spectroscopic investigations of poly(p-phenylene phosphine imide)s (2) are similar to those of polymer model compounds, suggesting formation of localized radical cations on the polymer chains and electronically insulating phosphorus atoms.

Organophosphorus π-Conjugated Materials

“…Lucht and co-workers have investigated the electron-donating properties of such iminophosphorane moieties in π-conjugated materials in detail to better understand the nature of the PN-bond in these systems as well as the degree of overlap with adjacent π-systems. , Their strong donor character has put the conjugated bis(iminophosphoranes) in the focus of organic electronics, as they might be utilized as efficient hole transport materials. Monomeric ( 252 , 253 ) as well as polymeric materials 254 (Chart ) are accessible by the Staudinger protocol using appropriate diazido precursors and triarylphosphanes, respectively, to afford the materials in good to high yields.…”

Synthesis and Intramolecular Charge-Transfer Interactions of a Donor–Acceptor Type Polymer Containing Ferrocene and TCNAQ Moieties

“…In other words, intramolecular charge-transfer interactions must be dominant in PFPA-Si. Because of the electron-donating property of phosphoranimine bond, 24 it would facilitate the intramolecular charge-transfer interactions between ferrocene and TCNAQ units in PFPA-Si. Because of the ICT interactions between ferrocene (and/or phosphoranimine) and TCNAQ units, upon scanning anodically, PFPA-Si exhibits three irreversible oxidation waves at the potentials of 0.62, 0.78, and 1.07 V (Figure S29).…”

Oxidation products of iminophosphorane and bis-iminophosphorane: An EPR study

“…The voltammogram of B para , already reported by Escobar et al [3] exhibits two reversible oxidation waves at E 0 = 0.04 and 0.53 V vs. SCE. The EPR spectrum (g = 2.0039) obtained by electrochemical oxidation at a potential slightly superior to the first wave is shown in Fig.…”

“…The pentavalent phosphorus P@N bonds are robust; they can be incorporated in conjugated polymers and are potentially able to give rise to organic conducting materials [3,4]. As shown by Escobar et al [3], the electron-donating capacity of the iminophosphorane bond is fundamental to explain the properties of these systems; in particular they showed that para bis-iminophosphorane B para possesses two reversible one-electron oxidations. The first chemical oxidation results in a shift of the optical absorption band consistent with the formation of the monocation.…”