Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom
Abstract Iminophosphoranes with the general formula (R3P═NR′) have great potential in synthetic chemistry as valuable precursors/intermediates in organic synthesis or as building blocks for various organic compounds. However, the synthetic approaches and conditions to prepare iminophosphoranes are s...
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Nature Portfolio
2025-01-01
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| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-024-01362-5 |
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| author | Tomaž Kotnik Antoine Debuigne Julien De Winter Matej Huš Albin Pintar Sebastijan Kovačič |
| author_facet | Tomaž Kotnik Antoine Debuigne Julien De Winter Matej Huš Albin Pintar Sebastijan Kovačič |
| author_sort | Tomaž Kotnik |
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| description | Abstract Iminophosphoranes with the general formula (R3P═NR′) have great potential in synthetic chemistry as valuable precursors/intermediates in organic synthesis or as building blocks for various organic compounds. However, the synthetic approaches and conditions to prepare iminophosphoranes are still poorly understood, limiting the utility of this chemistry for organic materials. In this article, a simple and efficient synthesis of previously unattainable poly(arylene iminophosphoranes) is reported. The azide-phosphine Staudinger polycondensation is used, and the reaction conditions are carefully studied, including consideration of light and air, the influence of solvent and temperature, and investigation of the electronic and steric effects of multiazides. The newly defined reaction conditions appear to be highly versatile, allowing the use of both electron-rich and electron-deficient arylazides for reaction with phosphines to synthesize a library of poly(arylene iminophosphorane) networks that exhibit exceptional thermal and oxidative stability. Interestingly, despite the ylidic-form of the iminophosphorane linkage as shown by theoretical calculations, these newly developed poly(arylene-iminophosphorane) networks exhibit semiconducting properties, such as absorption band edges up to 800 nm and optical band gaps in the range of 1.70 to 2.40 eV. Finally, we demonstrate the broad applicability of these polymers by processing them into glassy films, creating foam-like structures and synthesizing metallo-polymer hybrids. |
| format | Article |
| id | doaj-art-9eacb5b1a82645ff8d8b57bd26fcec6d |
| institution | Kabale University |
| issn | 2399-3669 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
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| series | Communications Chemistry |
| spelling | doaj-art-9eacb5b1a82645ff8d8b57bd26fcec6d2025-01-19T12:13:10ZengNature PortfolioCommunications Chemistry2399-36692025-01-018111110.1038/s42004-024-01362-5Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefromTomaž Kotnik0Antoine Debuigne1Julien De Winter2Matej Huš3Albin Pintar4Sebastijan Kovačič5National Institute of ChemistryChemistry Department, Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, University of Liege (ULiege)Organic Synthesis and Mass Spectrometry Laboratory (S2MOs), University of Mons-UMONSNational Institute of ChemistryNational Institute of ChemistryNational Institute of ChemistryAbstract Iminophosphoranes with the general formula (R3P═NR′) have great potential in synthetic chemistry as valuable precursors/intermediates in organic synthesis or as building blocks for various organic compounds. However, the synthetic approaches and conditions to prepare iminophosphoranes are still poorly understood, limiting the utility of this chemistry for organic materials. In this article, a simple and efficient synthesis of previously unattainable poly(arylene iminophosphoranes) is reported. The azide-phosphine Staudinger polycondensation is used, and the reaction conditions are carefully studied, including consideration of light and air, the influence of solvent and temperature, and investigation of the electronic and steric effects of multiazides. The newly defined reaction conditions appear to be highly versatile, allowing the use of both electron-rich and electron-deficient arylazides for reaction with phosphines to synthesize a library of poly(arylene iminophosphorane) networks that exhibit exceptional thermal and oxidative stability. Interestingly, despite the ylidic-form of the iminophosphorane linkage as shown by theoretical calculations, these newly developed poly(arylene-iminophosphorane) networks exhibit semiconducting properties, such as absorption band edges up to 800 nm and optical band gaps in the range of 1.70 to 2.40 eV. Finally, we demonstrate the broad applicability of these polymers by processing them into glassy films, creating foam-like structures and synthesizing metallo-polymer hybrids.https://doi.org/10.1038/s42004-024-01362-5 |
| spellingShingle | Tomaž Kotnik Antoine Debuigne Julien De Winter Matej Huš Albin Pintar Sebastijan Kovačič Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom Communications Chemistry |
| title | Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom |
| title_full | Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom |
| title_fullStr | Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom |
| title_full_unstemmed | Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom |
| title_short | Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom |
| title_sort | unlocking the potential of azide phosphine staudinger reaction for the synthesis of poly arylene iminophosphorane s and materials therefrom |
| url | https://doi.org/10.1038/s42004-024-01362-5 |
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