Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F24%3A00584536" target="_blank" >RIV/61388980:_____/24:00584536 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0352453" target="_blank" >https://hdl.handle.net/11104/0352453</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1080/14686996.2024.2322458" target="_blank" >10.1080/14686996.2024.2322458</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators

Popis výsledku v původním jazyce

A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)(4)) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (similar to 530 m(2) g(-1)). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best O-1(2) generating capability. Although the starting OxP-tetraamine precursor is a poor O-1(2) generator, its incorporation into OxP POPs leads to a significant enhancement of O-1(2) productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall O-1(2) production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Název v anglickém jazyce

Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators

Popis výsledku anglicky

A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)(4)) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (similar to 530 m(2) g(-1)). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best O-1(2) generating capability. Although the starting OxP-tetraamine precursor is a poor O-1(2) generator, its incorporation into OxP POPs leads to a significant enhancement of O-1(2) productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall O-1(2) production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Science and Technology of Advanced Materials

ISSN

1468-6996

e-ISSN

1878-5514

Svazek periodika

25

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

2322458

Kód UT WoS článku

001178915500001

EID výsledku v databázi Scopus

2-s2.0-85186405500