Metal complexes containing organic photoswitches are capable of modulating the steric and electronic environment around the metal center through photoisomerization,enabling their use in photoswitchable catalysis.Herei...Metal complexes containing organic photoswitches are capable of modulating the steric and electronic environment around the metal center through photoisomerization,enabling their use in photoswitchable catalysis.Herein,we design a new class of photoswitchable tripodal tetradentate ligands L1-L3 that can readily form air-stable Cu(Ⅰ)complexes(C1-PF_(6),C1-BF_(4),C2,C3).The design strategy integrates flexible spacers and phenylazopyrazole units in the same ligand framework that ensures efficient photoisomerization and sustained stability of the photoswitched state.The complexes were screened for catalyzing the CuAAC reaction between alkynes and azides and C1-PF_(6)was identified as a catalyst capable of exerting temporal control over the reaction through photoisomerization.Based on the optimized conditions and the substrate scope,the ZZZ(photoswitched)form of complex C1-PF_(6)exhibits substantially improved catalytic performance compared to its EEE(native)form.In this article,we describe detailed experimental and computational investigations aimed at understanding how photoisomerization regulates the catalytic activity of Cu(Ⅰ)complexes of arylazopyrazole-based tripodal tetradentate ligands.展开更多
基金DST Indo-Czech Republic Bilateral Scientific Research Cooperation,Ministry of Science and Technology,New Delhi,India(DST/INT/CZ/P-17/2019)the Science and Engineering Research Board(SERB),New Delhi for the financial support(CRG/2023/003861)+1 种基金SERB for funding(SB/SJF/2019-20/12,CRG/2022/001697)IISER Mohali for financial support,the departmental and central research facilities and other instruments(XRD,NMR,and HRMS including DST-FIST 400 MHz NMR facility,SR/FIST/CS-II/2019/94(C)TPN No.32545).
文摘Metal complexes containing organic photoswitches are capable of modulating the steric and electronic environment around the metal center through photoisomerization,enabling their use in photoswitchable catalysis.Herein,we design a new class of photoswitchable tripodal tetradentate ligands L1-L3 that can readily form air-stable Cu(Ⅰ)complexes(C1-PF_(6),C1-BF_(4),C2,C3).The design strategy integrates flexible spacers and phenylazopyrazole units in the same ligand framework that ensures efficient photoisomerization and sustained stability of the photoswitched state.The complexes were screened for catalyzing the CuAAC reaction between alkynes and azides and C1-PF_(6)was identified as a catalyst capable of exerting temporal control over the reaction through photoisomerization.Based on the optimized conditions and the substrate scope,the ZZZ(photoswitched)form of complex C1-PF_(6)exhibits substantially improved catalytic performance compared to its EEE(native)form.In this article,we describe detailed experimental and computational investigations aimed at understanding how photoisomerization regulates the catalytic activity of Cu(Ⅰ)complexes of arylazopyrazole-based tripodal tetradentate ligands.
