A guide for the design of functional polyaromatic organophosphorus materials
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-member...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2017
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| In: |
Chemistry - a European journal
Year: 2017, Volume: 23, Issue: 56, Pages: 13919-13928 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201701649 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/chem.201701649 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201701649 
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| Author Notes: | Philip Hindenberg, Alicia López‐Andarias, Frank Rominger, Abel de Cózar, and Carlos Romero‐Nieto |
| Summary: | 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. |
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| Item Description: | First published: 31 May 2017 Gesehen am 22.06.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201701649 |