Molecular Engineering of “Click”‐Phospholes Towards Self‐Assembled Luminescent Soft Materials

Abstract

Inspired by the self-assembled bilayer structures of natural amphiphilic phospholipids, a new class of highly luminescent "click"-phospholes with exocyclic alkynyl group at the phosphorus center is reported. These molecules can be easily functionalized with a self-assembly group to generate neutral "phosphole-lipids". This novel approach retains the versatile reactivity of the phosphorus center, allowing further engineering of the photophysical and self-assembly properties of the materials at a molecular level. The results of this study highlight the importance of being able to balance weak intermolecular interactions for controlling the self-assembly properties of soft materials. Only molecules with the appropriate set of intermolecular arrangement/interactions show both organogel and liquid crystal mesophases with well-ordered microstructures. Moreover, an effi cient energy transfer of the luminescent materials is demonstrated and applied in the detection of organic solvent vapors.

Phosphorus‐Containing Materials for Organic Electronics

“…Our group has also provided a recent contribution to the development of sensory materials with a cyclodextrin-based phosphole sensor. [36] In this study, we incorporated our previously reported "click" phosphole [37] and attached a cyclodextrin (28, Figure 12) known for its ability to host molecules and to induce water solubility to fluorophores. [38] This particular example was targeted at detecting molecular explosives, and the surrogate chosen for the study was picric acid.…”

Recent progress in luminescent liquid crystal materials: design, properties and application for linearly polarised emission

“…[21][22][23][24][25][26][27][28][29][30][31][32][33] Herein we review luminescent LC materials and discuss their LC and emission properties in the context of linearly polarised electroluminescence. [21][22][23][24][25][26][27][28][29][30][31][32][33] Herein we review luminescent LC materials and discuss their LC and emission properties in the context of linearly polarised electroluminescence.…”

Dithienophosphole‐Based Phosphinamides with Intriguing Self‐Assembly Behavior

“…Remarkably,inall previously studied non-hydrogen-bonded phospholes,f or which p-stacking dominates,t he molecules are assembled in af ace-to-face pattern, in which the p moieties align antiparallel to each other. [9] By contrast, the p moieties align parallel (i.e., in a syn-type fashion) in the new hydrogen-bonded system;t his feature was also found in 4c.However, as can be seen in Figure 3, the H-bonding in 4c follows az igzag pathway (dihedral angle PO-NH:4 7 8 8; Figure 4) instead of the nearly linear column found in 4a (dihedral angle PO-NH:1 318 8;F igure 4). The deviation from the linear assembly motif in 4c showcases an intriguing, novel structural feature of the hydrogen-bonded species:r otational flexibility of the phosphinamide bond.…”