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Post-Synthetically Elaborated BODIPY-Based Porous Organic Polymers (POPs) for the Photochemical Detoxification of a Sulfur Mustard Simulant.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2020 Oct 28; Vol. 142 (43), pp. 18554-18564. Date of Electronic Publication: 2020 Oct 19. - Publication Year :
- 2020
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Abstract
- Designing new materials for the effective detoxification of chemical warfare agents (CWAs) is of current interest given the recent use of CWAs. Although halogenated boron-dipyrromethene derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and 6 positions have been extensively explored as efficient photosensitizers for generating singlet oxygen ( <superscript>1</superscript> O <subscript>2</subscript> ) in homogeneous media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the difficulty of controlling polymerization processes through cross-coupling synthesis pathways. Our approach to overcome these difficulties and prepare halogenated BODIPY-based porous organic polymers ( X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthesis modification (PSM) of the parent hydrogenated polymer. Upon synthesis of both the parent polymer, H-BDP-POP , and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP , the BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m <superscript>2</superscript> · g <superscript>-1</superscript> , respectively. In addition, the insertion of heavy halogen atoms at the 2 and 6 positions of the BODIPY unit leads to the quenching of fluorescence (both polymer and solution-phase monomer forms) and the enhancement of phosphorescence (particularly for the iodo versions of the polymers and monomers), as a result of efficient intersystem crossing. The heterogeneous photocatalytic activities of both the parent POP and its derivatives for the detoxification of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), have been examined; the results show a significant enhancement in the generation of singlet oxygen ( <superscript>1</superscript> O <subscript>2</subscript> ). Both the bromination and iodination of H-BDP-POP served to shorten by 5-fold of the time needed for the selective and catalytic photo-oxidation of CEES to 2-chloroethyl ethyl sulfoxide (CEESO).
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 142
- Issue :
- 43
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 32981316
- Full Text :
- https://doi.org/10.1021/jacs.0c07784