Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides

IF 6.1 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2025-04-17 DOI:10.1039/d5qi00323g

Mateusz Janeta, Sławomir Szafert

{"title":"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides","authors":"Mateusz Janeta, Sławomir Szafert","doi":"10.1039/d5qi00323g","DOIUrl":null,"url":null,"abstract":"The incorporation of difluoroboron into the side arms of polyhedral oligomeric silsesquioxanes (POSSs) opens up new possibilities for the construction of metal-free photocatalysts with tailored properties. Herein, we report the design and synthesis of novel difluoroboron complexes of POSSs (POSS-tert-BF2, POSS-sal-BF2 and POSS-npht-BF2) derived from imine-functionalized POSSs, which were utilized as efficient photocatalysts. The complexes demonstrated exceptional photocatalytic performance in the aerobic oxidation of sulfides to sulfoxides, significantly outperforming their silsesquioxane-free counterparts. POSS-tert-BF2 demonstrated a high singlet oxygen quantum yield of 48%. This study highlights the feasibility of intramolecular cooperative activity in catalytic reactions and identifies key factors influencing its effectiveness. Furthermore, it underscores the potential of POSS as a versatile building block for the development of advanced photocatalytic materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":6.1000,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5qi00323g","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

The incorporation of difluoroboron into the side arms of polyhedral oligomeric silsesquioxanes (POSSs) opens up new possibilities for the construction of metal-free photocatalysts with tailored properties. Herein, we report the design and synthesis of novel difluoroboron complexes of POSSs (POSS-tert-BF₂, POSS-sal-BF₂ and POSS-npht-BF₂) derived from imine-functionalized POSSs, which were utilized as efficient photocatalysts. The complexes demonstrated exceptional photocatalytic performance in the aerobic oxidation of sulfides to sulfoxides, significantly outperforming their silsesquioxane-free counterparts. POSS-tert-BF₂ demonstrated a high singlet oxygen quantum yield of 48%. This study highlights the feasibility of intramolecular cooperative activity in catalytic reactions and identifies key factors influencing its effectiveness. Furthermore, it underscores the potential of POSS as a versatile building block for the development of advanced photocatalytic materials.

Abstract Image

查看原文本刊更多论文

多面体低聚硅烷基二氟硼络合物作为硫化物光氧化成硫醚的合作八位催化剂

在多面体低聚硅氧烷（POSSs）的侧臂中加入二氟硼，为构建具有定制性能的无金属光催化剂开辟了新的可能性。本文报道了以亚胺功能化POSSs为原料，设计合成了新型poss二氟硼配合物（POSS-tert-BF2、POSS-sal-BF2和POSS-npht-BF2），并将其用作高效光催化剂。该配合物在硫化物有氧氧化生成亚砜的过程中表现出优异的光催化性能，显著优于不含硅氧烷的配合物。POSS-tert-BF2单线态氧量子率高达48%。本研究强调了分子内协同活性在催化反应中的可行性，并确定了影响其有效性的关键因素。此外，它强调了POSS作为开发先进光催化材料的多功能构建块的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊