A new generation series of cyclometalated Ru(Ⅱ)polypyridyl complexes of the type[Ru(C^N)(N^N)_(2)]^(+),Ru1–Ru4,were rationally designed and synthesized,where N^N=2,2’-bipyridine(bpy)and dipyrido[3,2-d:2’,3’-f]qui...A new generation series of cyclometalated Ru(Ⅱ)polypyridyl complexes of the type[Ru(C^N)(N^N)_(2)]^(+),Ru1–Ru4,were rationally designed and synthesized,where N^N=2,2’-bipyridine(bpy)and dipyrido[3,2-d:2’,3’-f]quinoxaline(dpq)and C^N=deprotonated methyl 1-butyl-2-aryl-benzimidazolecarboxylate with p-CF_(3)C_(6)H_(4)or p-Me_(2)NC_(6)H_(4)substituents in the R3 position of the phenyl ring.The photophysical properties of Ru1–Ru4 revealed absorption maxima around 560 nm with an absorption up to 700 nm.The new Ru complexes were able to generate singlet oxygen(^(1)O_(2))upon green light irradiation in acetonitrile,with complexes containing the CF_(3)group,Ru1 and Ru3,being the best performers.Furthermore,Ru1 and Ru3 were also able to photogenerate hydroxyl radicals OH•.By having PSs capable of undergoing both typeⅠand typeⅡmechanisms,a broader range of cytotoxic effects is achieved.Ru1–Ru4 accumulated in membrane-rich compartments,including the cytoplasmic membrane,mitochondria,and endoplasmic reticulum in HeLa cells.Upon irradiation of Ru1 with green light,all these compartments were damaged in treated cells.Based on in vitro experiments,we deduced that the compound Ru1 under irradiation has the capability to disrupt phospholipid membranes directly.Additionally,differential scanning calorimetry of living cells also indicated damage of cytoplasmic/membrane proteins,ultimately leading to cell death via oncosis.展开更多
The design of new radical bridging ligands that can effectively promote strong magnetic coupling with LnIII ions needs to focus on radicals that are susceptible to synthetic modifications and bear diffuse spin density...The design of new radical bridging ligands that can effectively promote strong magnetic coupling with LnIII ions needs to focus on radicals that are susceptible to synthetic modifications and bear diffuse spin density on their donor atoms.To probe this,we introduced various substituents possessing different electron-withdrawing/donating capabilities into the redox-active s-tetrazinyl centre.This allowed for the systematic tuning of the redox and optoelectronic properties of the tetrazinyl ring.The effect of substitution on the strength of Ln–rad magnetic coupling was investigated on a series of radical-bridged Ln metallocene complexes featuring the 3,6-dimethyl-1,2,4,5-tetrazine(dmtz)and the 3,6-dimethoxy-1,2,4,5-tetrazine(dmeotz)ligands;[(Cp^(*)_(2)Ln)_(2)(dmtz^(·−))(THF)_(2)][BPh_(4)]·THF(Ln=Gd(1-Gd)or Dy(1-Dy);Cp^(*)=pentamethylcyclopentadienyl;THF=tetrahydrofuran)and[(Cp^(*)_(2)Ln)_(2)(dmeotz^(·−))(THF)][BPh_(4)](Ln=Gd(2-Gd)or Dy(2-Dy)).Cyclic voltammetry,UV-Vis absorption spectroscopy,SQUID magnetometry and ab initio as well as density functional theory(DFT)calculations are combined to underline the trends observed in this study,while comparisons with the unsubstituted 1,2,4,5-tetrazine(tz)and the 3,6-dichloro-1,2,4,5-tetrazine(dctz)are made.Notably,an intricate interplay between orbital overlap,ligand substituent effects and changes in the coordination environment is found to collectively dictate the magnitude of JGd–rad in the investigated systems.The strong magnetic coupling combined with highly anisotropic Dy^(Ⅲ)ions makes 1-Dy and 2-Dy exhibit slow magnetic relaxation in the absence of an external applied field.For 1-Dy,an opening of the hysteresis loop is observed with H_(c)=∼5000 Oe,one of the highest coercivities for a dinuclear organic radical-bridged single-molecule magnet.展开更多
基金supported by the Czech Science Foundation(grant 23-06316S)supported by the Spanish Ministerio de Ciencia e Innovación-Agencia Estatal de Investigación(MCI/AEI/10.13039/501100011033)+2 种基金FEDER funds(project PID2021-122850NB-I00)Fundación Séneca-CARM(project 21989/PI/22)Fundación Séneca-CARM for a grant(project 21426/FPI/20).
文摘A new generation series of cyclometalated Ru(Ⅱ)polypyridyl complexes of the type[Ru(C^N)(N^N)_(2)]^(+),Ru1–Ru4,were rationally designed and synthesized,where N^N=2,2’-bipyridine(bpy)and dipyrido[3,2-d:2’,3’-f]quinoxaline(dpq)and C^N=deprotonated methyl 1-butyl-2-aryl-benzimidazolecarboxylate with p-CF_(3)C_(6)H_(4)or p-Me_(2)NC_(6)H_(4)substituents in the R3 position of the phenyl ring.The photophysical properties of Ru1–Ru4 revealed absorption maxima around 560 nm with an absorption up to 700 nm.The new Ru complexes were able to generate singlet oxygen(^(1)O_(2))upon green light irradiation in acetonitrile,with complexes containing the CF_(3)group,Ru1 and Ru3,being the best performers.Furthermore,Ru1 and Ru3 were also able to photogenerate hydroxyl radicals OH•.By having PSs capable of undergoing both typeⅠand typeⅡmechanisms,a broader range of cytotoxic effects is achieved.Ru1–Ru4 accumulated in membrane-rich compartments,including the cytoplasmic membrane,mitochondria,and endoplasmic reticulum in HeLa cells.Upon irradiation of Ru1 with green light,all these compartments were damaged in treated cells.Based on in vitro experiments,we deduced that the compound Ru1 under irradiation has the capability to disrupt phospholipid membranes directly.Additionally,differential scanning calorimetry of living cells also indicated damage of cytoplasmic/membrane proteins,ultimately leading to cell death via oncosis.
文摘The design of new radical bridging ligands that can effectively promote strong magnetic coupling with LnIII ions needs to focus on radicals that are susceptible to synthetic modifications and bear diffuse spin density on their donor atoms.To probe this,we introduced various substituents possessing different electron-withdrawing/donating capabilities into the redox-active s-tetrazinyl centre.This allowed for the systematic tuning of the redox and optoelectronic properties of the tetrazinyl ring.The effect of substitution on the strength of Ln–rad magnetic coupling was investigated on a series of radical-bridged Ln metallocene complexes featuring the 3,6-dimethyl-1,2,4,5-tetrazine(dmtz)and the 3,6-dimethoxy-1,2,4,5-tetrazine(dmeotz)ligands;[(Cp^(*)_(2)Ln)_(2)(dmtz^(·−))(THF)_(2)][BPh_(4)]·THF(Ln=Gd(1-Gd)or Dy(1-Dy);Cp^(*)=pentamethylcyclopentadienyl;THF=tetrahydrofuran)and[(Cp^(*)_(2)Ln)_(2)(dmeotz^(·−))(THF)][BPh_(4)](Ln=Gd(2-Gd)or Dy(2-Dy)).Cyclic voltammetry,UV-Vis absorption spectroscopy,SQUID magnetometry and ab initio as well as density functional theory(DFT)calculations are combined to underline the trends observed in this study,while comparisons with the unsubstituted 1,2,4,5-tetrazine(tz)and the 3,6-dichloro-1,2,4,5-tetrazine(dctz)are made.Notably,an intricate interplay between orbital overlap,ligand substituent effects and changes in the coordination environment is found to collectively dictate the magnitude of JGd–rad in the investigated systems.The strong magnetic coupling combined with highly anisotropic Dy^(Ⅲ)ions makes 1-Dy and 2-Dy exhibit slow magnetic relaxation in the absence of an external applied field.For 1-Dy,an opening of the hysteresis loop is observed with H_(c)=∼5000 Oe,one of the highest coercivities for a dinuclear organic radical-bridged single-molecule magnet.
