Incorporating Phosphaalkenes into Oligoacetylenes

Abstract

Mind the gap! Replacing the two terminal carbon atoms of a tetrayne‐linked bis‐alkene by two phosphorus centers leads to a decrease of the HOMO–LUMO gap by 0.5 eV. The acetylenic phosphaalkenes are accessible from an ambivalent carbene‐type C5 intermediate and are shown to be viable building blocks for the construction of elaborate phosphorus‐ and carbon‐rich molecules (see picture; C gray, P purple).

Organophosphorus derivatives for electronic devices

“…The present article does not aim to review all the different kinds of organophosphorus based materials, 7 but only those who have been inserted into electronic devices (organic lightemitting diode (OLED), organic photovoltaic cell (OPV cell), dye-sensitized solar cell (DSSC), organic field-effect transistors (OFET), electrochromic cells). Indeed, despite the interesting work on some organophosphorus -conjugated materials like phosphalkenes 8 or diphosphenes 9 none of these derivatives have ever been used in electronic device, probably because of poor stability of the C=P and P=P bond. Actually five types of organophosphorus material have made the cut: triaryl phosphines, phosphazenes, phospholes, phosphetes and diphosphacyclobutanes (Fig.…”

Phosphines and related C–P bonded compounds

“…345 A successful protocol has been developed for the introduction of stable phosphaalkene units into oligoalkynes, leading to compounds of types (162) and (163), a new class of p-conjugated molecules. 346 Also reported are routes to the planar chiral 1-phosphaethenyl-2-phosphinoferrocenes (164), from the reactions of optically active 2-phosphinoferrocenecarboxaldehydes with Mes*P(Li)SiMe 3 in THF, 347 and the bidentate ligands (165), incorporating an acyclic phosphaalkene unit. 348 Chlorophosphaalkenylstibines, e.g., (166), have been obtained from the reactions of Mes*PQ C(SiMe 3 )Li or the phosphaalkene carbenoid Mes*PQC(Cl)Li with fluorostibines.…”

Cooperative Gold Nanoparticle Stabilization by Acetylenic Phosphaalkenes

“…However, the picture changes dramatically when an additional acetylene unit is introduced at the phosphaalkene moiety and one of the resulting acetylenic phosphaalkenes (APAs) 4 – 7 are employed during NP fabrication. For example, following a procedure by Wallner et al,[ 11b ] a mixture of HAuCl 4 and C , C -diacetylenic phosphaalkene 7 [ 12 ] was reduced with Et 3 SiH and AuNP formation was apparent from the immediate appearance of a dark red SPR. [ 13 ] For the determination of the factors that govern NP fabrication, it was necessary to confirm that NP stabilization proceeded through the P=C unit, and not through acetylides (similar to type A, Figure 1 ) that could arise from desilylation of 7 .…”