A guide for the design of functional polyaromatic organophosphorus materials

• Verfasst von: Hindenberg, Philip [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Romero-Nieto, Carlos [VerfasserIn]
• Titel: A guide for the design of functional polyaromatic organophosphorus materials
• Verf.angabe: Philip Hindenberg, Alicia López‐Andarias, Frank Rominger, Abel de Cózar, and Carlos Romero‐Nieto
• Jahr: 2017
• Umfang: 10 S.
• Fussnoten: First published: 31 May 2017 ; Gesehen am 22.06.2018
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2017
• Band/Heft Quelle: 23(2017), 56, Seite 13919-13928
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201701649
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: density functional calculations
• Sach-SW: heterocycles
• Sach-SW: optoelectronic properties
• Sach-SW: organophosphorus materials
• Sach-SW: reaction mechanisms
• K10plus-PPN: 1576775704

Abstract

The impact of integrating six-membered phosphorus heterocycles into a poly(hetero)aromatic materials is investigated. Mechanistic studies reveal the key synthetic requirements to embed the latter phosphorus heterocycles in polyaromatic molecules. DFT calculations indicate that introducing six-membered phosphorus rings into π-extended molecules induces a particular electron distribution over the π-extended system. Electrochemical investigations confirm that inserting six-membered phosphacycles into polyaromatics triggers ambipolar redox behavior. Steady-state spectroscopy reveals that fusing pyrroles with phosphorus-containing polyaromatic molecules induces fluorescence quantum yields as high as 0.8, whereas transient absorption spectroscopy demonstrates that fusing thiophenes promote the formation of non-emissive triplet-excited states. As a whole, the optoelectronic properties of fused phosphorus-containing materials give rise to promising performances in photoelectrochemical cells. Moreover, X-ray analyses confirm that the 3D arrangement in the solid state of polyaromatic systems containing six-membered phosphorus rings can be tailored through post-functionalization of the phosphorus center. Altogether, this investigation sets the bedrock for the design of a new generation of highly functional polyaromatic organophosphorus materials, keeping control over their electrochemical properties, fluorescence features, photo-induced excited states, and 3D molecular arrangement.