A microwave mediated solvent free one pot synthesis of formazans is developed using the solid acid, KHSO4. The products were obtained in a short reaction time in high yield. This study was undertaken to find an altern...A microwave mediated solvent free one pot synthesis of formazans is developed using the solid acid, KHSO4. The products were obtained in a short reaction time in high yield. This study was undertaken to find an alternative and green method for the synthesis of formazans in the absence of corrosive mineral acids, buffered solutions and volatile organic compounds (VOCs).展开更多
The capture,storage,and release of CO_(2)is one of the most pressing issues in chemistry.Herein,we designed bis(formazanate)magnesium complexes as precursors,which were synthesized by straightforward transamination be...The capture,storage,and release of CO_(2)is one of the most pressing issues in chemistry.Herein,we designed bis(formazanate)magnesium complexes as precursors,which were synthesized by straightforward transamination between the neutral formazan[PhNNC(4-tBuPh)NNHPh](LH)and[Mg{N(SiMe_(3))_(2)}_(2)].Depending on the solvent,either the homoleptic complex[L_(2)Mg]or the thf-coordinated complex[L_(2)Mg(thf)]was isolated.Reaction of the solvent-free complex[L_(2)Mg]with CO_(2)led to stoichiometric insertion into one of the four Mg–Nbonds with concomitant rearrangement of the ligand scaffold which adopts a trinuclear cagelike structure.The insertion reaction is reversible depending on thermolysis or treatment with tetrahydrofuran,which is corroborated by density functional theory calculations.This showcases the first example of reversible uptake of CO_(2)by an s-block coordination compound.展开更多
The small molecular second near-infrared(NIR-Ⅱ, 1000–1700 nm) dye-based nanotheranostics can concurrently combine deep-tissue photodiagnosis with in situ phototherapy, which occupies a vital position in the early de...The small molecular second near-infrared(NIR-Ⅱ, 1000–1700 nm) dye-based nanotheranostics can concurrently combine deep-tissue photodiagnosis with in situ phototherapy, which occupies a vital position in the early detection and precise treatment of tumors. However, the development of small molecular NIR-Ⅱ dyes is still challenging due to the limited electron acceptors and cumbersome synthetic routes.Herein, we report a novel molecular electron acceptor, boron difluoride formazanate(BDF). Based on BDF, a new small molecular NIR-Ⅱ dye BDF1005 is designed and synthesized with strong NIR-I absorption at 768 nm and bright NIR-Ⅱ peak emission at 1034 nm. In vitro and in vivo experiments demonstrate that BDF1005-based nanotheranostics can be applied for NIR-Ⅱ fluorescence imaging-guided photothermal therapy of 4T1 tumor-bearing mice. Under 808 nm laser irradiation, tumor growth can be effectively inhibited. This work opens up a new road for the exploitation of NIR-Ⅱ small molecular dyes for cancer phototheranostics.展开更多
文摘A microwave mediated solvent free one pot synthesis of formazans is developed using the solid acid, KHSO4. The products were obtained in a short reaction time in high yield. This study was undertaken to find an alternative and green method for the synthesis of formazans in the absence of corrosive mineral acids, buffered solutions and volatile organic compounds (VOCs).
基金D.J.thanks the China Scholarship Council(grant no.201906030178)for generous supportWe also acknowledge support by the state of Baden-Württemberg through bwHPC and DFG through grant no.INST 40/467-1 FUGG(JUSTUS cluster).
文摘The capture,storage,and release of CO_(2)is one of the most pressing issues in chemistry.Herein,we designed bis(formazanate)magnesium complexes as precursors,which were synthesized by straightforward transamination between the neutral formazan[PhNNC(4-tBuPh)NNHPh](LH)and[Mg{N(SiMe_(3))_(2)}_(2)].Depending on the solvent,either the homoleptic complex[L_(2)Mg]or the thf-coordinated complex[L_(2)Mg(thf)]was isolated.Reaction of the solvent-free complex[L_(2)Mg]with CO_(2)led to stoichiometric insertion into one of the four Mg–Nbonds with concomitant rearrangement of the ligand scaffold which adopts a trinuclear cagelike structure.The insertion reaction is reversible depending on thermolysis or treatment with tetrahydrofuran,which is corroborated by density functional theory calculations.This showcases the first example of reversible uptake of CO_(2)by an s-block coordination compound.
基金supported by the National Natural Science Foundation of China (No. 61775095)Natural Science Foundation of Jiangsu Province (No. BK20200092)+3 种基金Jiangsu Province Policy Guidance Plan (No. BZ2019014)Natural Science Foundation of Shandong Province (No. ZR2020KB018)‘Taishan scholars’ construction special fund of Shandong Provincethe High-Performance Computing Center in Nanjing Tech University for supporting the computational resources
文摘The small molecular second near-infrared(NIR-Ⅱ, 1000–1700 nm) dye-based nanotheranostics can concurrently combine deep-tissue photodiagnosis with in situ phototherapy, which occupies a vital position in the early detection and precise treatment of tumors. However, the development of small molecular NIR-Ⅱ dyes is still challenging due to the limited electron acceptors and cumbersome synthetic routes.Herein, we report a novel molecular electron acceptor, boron difluoride formazanate(BDF). Based on BDF, a new small molecular NIR-Ⅱ dye BDF1005 is designed and synthesized with strong NIR-I absorption at 768 nm and bright NIR-Ⅱ peak emission at 1034 nm. In vitro and in vivo experiments demonstrate that BDF1005-based nanotheranostics can be applied for NIR-Ⅱ fluorescence imaging-guided photothermal therapy of 4T1 tumor-bearing mice. Under 808 nm laser irradiation, tumor growth can be effectively inhibited. This work opens up a new road for the exploitation of NIR-Ⅱ small molecular dyes for cancer phototheranostics.
