Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2...Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.展开更多
Organic dyes with strong absorption in the second near-infrared(NIR-II)window(1000-1700 nm)have multiple applications.However,the design and synthesis of stable NIR-II absorbing organic dyes are very challenging and c...Organic dyes with strong absorption in the second near-infrared(NIR-II)window(1000-1700 nm)have multiple applications.However,the design and synthesis of stable NIR-II absorbing organic dyes are very challenging and constantly defy our synthetic ability.In this work,we have successfully synthesized a series of soluble and stable fused thienoisoindigo(nThIID)ribbons.The absorption maximum(λ_(max))of the ribbons increases from 644 nm of 1ThIID to 1252 nm of 6ThIID.Importantly,nThIIDs with n≥4 all display strong absorption in the NIR-II window with molar extinction coefficients(ε_(max))greater than 105 L mol^(−1)cm^(−1)atλmax.These molecules are promising photothermal conversion dyes with photothermal conversion efficiencies of ca.60%under 1064 nm laser irradiation.展开更多
基金Financial support was provided by the the National Natural Science Foundation of China(nos.21822108,21822303,21801176,21772129,and 21772020)the Fok Ying Tung Education Foundation(no.161013)+1 种基金Sichuan Science and Technology Program(nos.2019YJ0379 and 20CXTD0112)the Fundamental Research Funds for the Central Universities.
文摘Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.
基金This work was supported by the National Natural Science Foundation of China(grant nos.22005211 and 52121002).Prof.Yonghao Zheng is acknowledged for his help on the analysis of VT-EPR results.
文摘Organic dyes with strong absorption in the second near-infrared(NIR-II)window(1000-1700 nm)have multiple applications.However,the design and synthesis of stable NIR-II absorbing organic dyes are very challenging and constantly defy our synthetic ability.In this work,we have successfully synthesized a series of soluble and stable fused thienoisoindigo(nThIID)ribbons.The absorption maximum(λ_(max))of the ribbons increases from 644 nm of 1ThIID to 1252 nm of 6ThIID.Importantly,nThIIDs with n≥4 all display strong absorption in the NIR-II window with molar extinction coefficients(ε_(max))greater than 105 L mol^(−1)cm^(−1)atλmax.These molecules are promising photothermal conversion dyes with photothermal conversion efficiencies of ca.60%under 1064 nm laser irradiation.
