Fusion of Phosphole and 1,1′‐Biacenaphthene: Phosphorus(V)‐Containing Extended π‐Systems with High Electron Affinity and Electron Mobility

Phosphorus‐Containing Materials for Organic Electronics

“…More recently, work has been extended in this field by Matano et al., who reached electron mobilities of up to 2.4×10 −3 cm 2 V −1 s −1 for 45 (Figure 18). 57 While these discussed charge mobilities were determined by time‐of‐flight methods55 and yet have to be validated in device applications, the development towards higher mobility has been a useful tool for fine‐tuning properties and ultimately achieving applications in organic electronics.…”

Redox‐Induced Reversible PP Bond Formation to Generate an Organometallic σ4λ4‐1,2‐Biphosphane Dication

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Many well-established methods exist for fine-tuning the properties of phosphorus compounds, and these allow the creation of tailored stereoelectronic environments that exert exact and predefined control over systems for catalysis [1] or molecular electronics. [2] In principle, the capacity to change the properties of a phosphorus center actively during a process creates further important potential, such as on-off switching in catalysis, [3] or profound gating of the properties of electronic materials. [4] Studies of how phosphorus centers can be efficiently modulated using ferrocenes, [5] cobaltocenes, [6] TTF derivatives, [7] or other redox-active groups have appeared; however, these redox-active groups are often spatially close to the phosphorus center, so the electronic outcome of the redox change can be conflated with significant steric effects.

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Tunable Photochromism in Air‐Stable, Robust Dithienylethene‐Containing Phospholes through Modifications at the Phosphorus Center

“…[2][3][4] On the other hand, there has been an increasing interest in the study of phosphole-containing materials due to their capability to serve as organic light-emitting diodes (OLEDs) and electron transport materials in organic devices. [5][6][7] The trivalent phosphorus center in the phosphole adopts a pyramidal geometry and the lone pair of phosphorus displays a high degree of s character, which cannot be efficiently delocalized in the butadiene moiety of the phosphole. [5,8] So it provides a reactive phosphorus center that can be functionalized by various chemical modifications.…”

“…As an extension of our continuing interests in designing various functionalized photochromic materials and in tuning the photochromism, [2] we hypothesized that, by utilizing this unique characteristic of phospholes, the electrochemistry, photophysics, and photochromism of the diarylethenes could be controlled through the rational design of the phosphole moiety without tedious modification of the diarylethene framework. To the best of our knowledge, although phosphole-containing materials have attracted growing interest and have been studied by a number of groups, [5][6][7][9][10][11] the integration of the phosphole moiety in the photochromic dithienylethene backbone has not been reported. Herein, we report the syntheses and photochromic properties of a series of dithienylethenecontaining phospholes.…”

“…The 31 P{ 1 H} NMR signals of 1-5 are found at d = 26.0, 33.4, 21.6, À15.6, and 18.2 ppm, respectively, values typical of the corresponding phosphole derivatives. [5][6][7][9][10][11] The 11 B NMR signal at d = À36.1 ppm was further indicative of the formation of 3. [9] Single crystals suitable for X-ray crystallography were obtained for 1, 2, and 5.…”