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Article: BODIPY-Based Polymers of Intrinsic Microporosity for the Photocatalytic Detoxification of a Chemical Threat

TitleBODIPY-Based Polymers of Intrinsic Microporosity for the Photocatalytic Detoxification of a Chemical Threat
Authors
KeywordsBODIPY
charge and energy transfers
photocatalysis
polymers of intrinsic microporosity
singlet oxygen
sulfur-mustard detoxification
Issue Date2022
Citation
ACS Applied Materials and Interfaces, 2022, v. 14, n. 10, p. 12596-12605 How to Cite?
AbstractEffective heterogeneous photocatalysts capable of detoxifying chemical threats in practical settings must exhibit outstanding device integrity. We report a copolymerization that yields robust, porous, processible, chromophoric BODIPY (BDP; boron-dipyrromethene)-containing polymers of intrinsic microporosity (BDP-PIMs). Installation of a pentafluorophenyl at the meso position of a BDP produced reactive monomer that when combined with 5,5,6,6-tetrahydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane (TTSBI) and tetrafluoroterephthalonitrile (TFTPN) yields PIM-1. Postsynthetic modification of these polymers yields Br-BDP-PIM-1a and -1b─polymers containing bromine at the 2,6-positions. Remarkably, the brominated polymers display porosity and processability features similar to those of H-BDP-PIMs. Gas adsorption reveals molecular-scale porosity and Brunette-Emmet-Teller surface areas as high as 680 m2 g-1. Electronic absorption spectra reveal charge-transfer (CT) bands centered at 660 nm, while bands arising from local excitations, LE, of BDP and TFTPN units are at 530 and 430 nm, respectively. Fluorescence spectra of the polymers reveal a Förster resonance energy-transfer (FRET) pathway to BDP units when TFTPN units are excited at 430 nm; weak phosphorescence at room temperature indicates a singlet-to-triplet intersystem crossing. The low-lying triplet state is well positioned energetically to sensitize the conversion of ground-state (triplet) molecular oxygen to electronically excited singlet oxygen. Photosensitization capabilities of these polymers toward singlet-oxygen-driven detoxification of a sulfur-mustard simulant 2-chloroethyl ethyl sulfide (CEES) have been examined. While excitation of CT and LEBDP bands yields weak catalytic activity (t1/2 > 15 min), excitation to higher energy states of TFTPN induces significant increases in photoactivity (t1/2 ≅ 5 min). The increase is attributable to (i) enhanced light collection, (ii) FRET between TFTPN and BDP, (iii) the presence of heavy atoms (bromine) having large spin-orbit coupling energies that can facilitate intersystem crossing from donor-acceptor CT-, FRET-, or LE-generated BDP singlet states to BDP-related triplet states, and (iv) polymer triplet excited-state sensitization of the formation of CEES-reactive, singlet oxygen.
Persistent Identifierhttp://hdl.handle.net/10722/332254
ISSN
2023 Impact Factor: 8.3
2023 SCImago Journal Rankings: 2.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorAtilgan, Ahmet-
dc.contributor.authorBeldjoudi, Yassine-
dc.contributor.authorYu, Jierui-
dc.contributor.authorKirlikovali, Kent O.-
dc.contributor.authorWeber, Jacob A.-
dc.contributor.authorLiu, Jian-
dc.contributor.authorJung, Dahee-
dc.contributor.authorDeria, Pravas-
dc.contributor.authorIslamoglu, Timur-
dc.contributor.authorStoddart, J. Fraser-
dc.contributor.authorFarha, Omar K.-
dc.contributor.authorHupp, Joseph T.-
dc.date.accessioned2023-10-06T05:10:03Z-
dc.date.available2023-10-06T05:10:03Z-
dc.date.issued2022-
dc.identifier.citationACS Applied Materials and Interfaces, 2022, v. 14, n. 10, p. 12596-12605-
dc.identifier.issn1944-8244-
dc.identifier.urihttp://hdl.handle.net/10722/332254-
dc.description.abstractEffective heterogeneous photocatalysts capable of detoxifying chemical threats in practical settings must exhibit outstanding device integrity. We report a copolymerization that yields robust, porous, processible, chromophoric BODIPY (BDP; boron-dipyrromethene)-containing polymers of intrinsic microporosity (BDP-PIMs). Installation of a pentafluorophenyl at the meso position of a BDP produced reactive monomer that when combined with 5,5,6,6-tetrahydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane (TTSBI) and tetrafluoroterephthalonitrile (TFTPN) yields PIM-1. Postsynthetic modification of these polymers yields Br-BDP-PIM-1a and -1b─polymers containing bromine at the 2,6-positions. Remarkably, the brominated polymers display porosity and processability features similar to those of H-BDP-PIMs. Gas adsorption reveals molecular-scale porosity and Brunette-Emmet-Teller surface areas as high as 680 m2 g-1. Electronic absorption spectra reveal charge-transfer (CT) bands centered at 660 nm, while bands arising from local excitations, LE, of BDP and TFTPN units are at 530 and 430 nm, respectively. Fluorescence spectra of the polymers reveal a Förster resonance energy-transfer (FRET) pathway to BDP units when TFTPN units are excited at 430 nm; weak phosphorescence at room temperature indicates a singlet-to-triplet intersystem crossing. The low-lying triplet state is well positioned energetically to sensitize the conversion of ground-state (triplet) molecular oxygen to electronically excited singlet oxygen. Photosensitization capabilities of these polymers toward singlet-oxygen-driven detoxification of a sulfur-mustard simulant 2-chloroethyl ethyl sulfide (CEES) have been examined. While excitation of CT and LEBDP bands yields weak catalytic activity (t1/2 > 15 min), excitation to higher energy states of TFTPN induces significant increases in photoactivity (t1/2 ≅ 5 min). The increase is attributable to (i) enhanced light collection, (ii) FRET between TFTPN and BDP, (iii) the presence of heavy atoms (bromine) having large spin-orbit coupling energies that can facilitate intersystem crossing from donor-acceptor CT-, FRET-, or LE-generated BDP singlet states to BDP-related triplet states, and (iv) polymer triplet excited-state sensitization of the formation of CEES-reactive, singlet oxygen.-
dc.languageeng-
dc.relation.ispartofACS Applied Materials and Interfaces-
dc.subjectBODIPY-
dc.subjectcharge and energy transfers-
dc.subjectphotocatalysis-
dc.subjectpolymers of intrinsic microporosity-
dc.subjectsinglet oxygen-
dc.subjectsulfur-mustard detoxification-
dc.titleBODIPY-Based Polymers of Intrinsic Microporosity for the Photocatalytic Detoxification of a Chemical Threat-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/acsami.1c21750-
dc.identifier.pmid35234435-
dc.identifier.scopuseid_2-s2.0-85126090045-
dc.identifier.volume14-
dc.identifier.issue10-
dc.identifier.spage12596-
dc.identifier.epage12605-
dc.identifier.eissn1944-8252-
dc.identifier.isiWOS:000787549000057-

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