Siloxane−Triarylamine Hybrids: Discrete Room Temperature Liquid Triarylamines via the Piers−Rubinsztajn Reaction

Abstract

A series of room temperature liquid siloxane-triarylamine hybrids were synthesized using the Piers-Rubinsztajn reaction. These materials displayed well behaved electrochemical oxidation and low T(g)'s and were free-flowing liquids. The interaction between the Lewis acidic tris(pentafluorophenyl)borane catalyst and the Lewis basic starting triarylamine substrate was also investigated by steady state UV-vis spectroscopy and (19)F NMR.

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

“…The reaction is proposed to proceed with the formation of the silyloxonium cation. [45][46][47] Comparison between the NHSG and Piers-Rubinsztajn reactions Similarities of the reactions As described above, both the NHSG and Piers-Rubinsztajn reactions are useful for siloxane synthesis. In the case of alkoxysilanes derived from primary alcohols, H is preferably transferred to silicon.…”

“…The reaction has been applied to the preparation of siloxane-triarylamine hybrid materials for organic electronic devices. [45][46][47] Comparison between the NHSG and Piers-Rubinsztajn reactions Similarities of the reactions As described above, both the NHSG and Piers-Rubinsztajn reactions are useful for siloxane synthesis. Both reactions are quite similar in terms of 1) a reaction of alkoxysilane involving CÀO bond cleavage, 2) Lewis acid catalyzed siloxane formation, and 3) competition of group-exchanging reactions with siloxane-bond formation ( Table 2).…”

Solution-Processed Blue/Deep Blue and White Phosphorescent Organic Light-Emitting Diodes (PhOLEDs) Hosted by a Polysiloxane Derivative with Pendant mCP (1,3-bis(9-carbazolyl)benzene)

“…To improve thermal, electrochemical, and morphological stability and to enhance the film-forming ability of organic 5 semiconductors, siloxanes have been combined with organic molecular structures; this has a minimal effect on the electronic properties of the materials. [42][43][44][45][46][47] Previously a polytetraphenylsilane derivative with a pendant carbazole unit 48 and a bipolar poly(phenylcarbazole-alt-triphenylphosphine oxide) siloxane 49 have served as hosts for blue and deep blue phosphors. We now report the synthesis of the new mCP-modified polysiloxane (PmCPSi) which incorporates mCP moieties as pendant groups linked via a phenoxy spacer unit, which is designed to remove the detrimental steric crowding between the siloxane backbone and the mCP units observed in a previous oligomer.…”

Remarkable Enhancement of the Hole Mobility in Several Organic Small‐Molecules, Polymers, and Small‐Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p‐Dopant B(C6F5)3

“…Although the latter picture may appear to rule out ground‐state integer electron transfer from diF‐TESADT and/or PTAA to B(C 6 F 5 ) 3 , a recent study suggests that such processes may be at play due to the significantly deeper LUMO energy (−4.81 eV) of B(C 6 F 5 ) 3 , although it is unclear how this value was derived [see Figure c] . Alternatively, Lewis acid/base interactions between B(C 6 F 5 ) 3 and certain chemical species within the blend may take place . If integer electron transfer took place, it would most likely involve the transfer of an electron from the organic semiconductor(s) to B(C 6 F 5 ) 3 resulting in the formation of radical cation(s) and p‐doping.…”