A Guide for the Design of Functional Polyaromatic Organophosphorus Materials

作者：Hindenberg Philip; Lopez Andarias Alicia; Rominger Frank; de Cozar Abel^*; Romero Nieto Carlos^*

来源：Chemistry - A European Journal, 2017, 23(56): 13919-13928.

DOI：10.1002/chem.201701649

• density functional calculations
• optoelectronic properties
• organophosphorus materials
• reaction mechanisms
• heterocycles

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 pi-extended molecules induces a particular electron distribution over the -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.

• 出版日期2017-10-9