The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential...The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.展开更多
Two isostructural lanthanide complexes, [Tb(salen)2]3·3C2H9N2·4CH4O(1) and [Er(salen)2]3·3C2H9N2·2CH4O(2), where H2 salen = N,N'-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in sit...Two isostructural lanthanide complexes, [Tb(salen)2]3·3C2H9N2·4CH4O(1) and [Er(salen)2]3·3C2H9N2·2CH4O(2), where H2 salen = N,N'-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in situ synthesized under solvothermal conditions and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analysis, and magnetic analysis. Single-crystal X-ray diffraction indicates that the complexes crystallize in monoclinic C121 space group. Each lanthanide center is coordinated with four oxygen and four nitrogen atoms from two salen^2- ligands, forming distorted square antiprism geometry. Both 1 and 2 exhibit obvious slow magnetization relaxation under an applied 2 kOe magnetic field.展开更多
Achieving non-centrosymmetric(NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical(NLO) materials due to the conflicting requirements of high second-harmonic generation(SH...Achieving non-centrosymmetric(NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical(NLO) materials due to the conflicting requirements of high second-harmonic generation(SHG) response,wide bandgap,and phase-matching capabilities.Herein,we propose a triplesite modulation strategy by synergistically tailoring the A-site cations(2-methylimidazole cation/1-ethyl-3-methylimidazole cation),B-site metals(Sn^(2+)/Pb^(2+)),and X-site halogens(Cl/Br),which effectively disrupts lattice symmetry and enables NCS crystallization.Our results demonstrate a strong SHG response,an expanded optical bandgap and increased birefringence.The optimized compound C_(6)H_(11)N_(2)PbCl_(3) exhibits a moderately strong SHG efficiency of 3.8 × KDP,a wide bandgap(3.87 eV),and enhanced birefringence(0.139@1064 nm),surpassing majority hybrid NLO materials.The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals,facilitating the integration of various aromatic heterocyclic cations.This research provides a robust strategic framework for the development of advanced NLO materials.展开更多
Three isostructural lanthanide complexes,namely[Ln(L)_(3)·CH_(3) OH](Ln=Tb(1),Dy(2),Ho(3),HL=N-(pyridin-2-ylcarbamothioyl)benzamide),were successfully synthesized and characterized by IR,UV,elemental analysis,sin...Three isostructural lanthanide complexes,namely[Ln(L)_(3)·CH_(3) OH](Ln=Tb(1),Dy(2),Ho(3),HL=N-(pyridin-2-ylcarbamothioyl)benzamide),were successfully synthesized and characterized by IR,UV,elemental analysis,single-crystal X-ray diffraction and DNA-biding analysis.X-ray single-crystal diffractions show that the family of lanthanide complexes crystallizes in monoclinic C2/c space group.Each lanthanide atom is coordinated with three carbonyl-O atoms,three pyridyl-N atoms and three imine-N atoms from three distinct L^(-1) ligands,forming a distorted tricapped trigonal prism.The binding properties of complexes with ct-DNA were studied by simulating the physiological environment of human body.The results suggest that compounds could bind with ct-DNA through interaction under a spontaneous process.展开更多
基金Project supported by the National Natural Science Foundation of China(52062034)the National Key Research and Development Program of China(2019YFC0605002)。
文摘The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.
基金supported by the National Natural Science Foundation of China(21101090 and 21561021)
文摘Two isostructural lanthanide complexes, [Tb(salen)2]3·3C2H9N2·4CH4O(1) and [Er(salen)2]3·3C2H9N2·2CH4O(2), where H2 salen = N,N'-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in situ synthesized under solvothermal conditions and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analysis, and magnetic analysis. Single-crystal X-ray diffraction indicates that the complexes crystallize in monoclinic C121 space group. Each lanthanide center is coordinated with four oxygen and four nitrogen atoms from two salen^2- ligands, forming distorted square antiprism geometry. Both 1 and 2 exhibit obvious slow magnetization relaxation under an applied 2 kOe magnetic field.
基金supported by the National Natural Science Foundation of China (No.22275052)Department of Science and Technology of Hubei Province (Nos.2025AFA111 and 2024CSA076)。
文摘Achieving non-centrosymmetric(NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical(NLO) materials due to the conflicting requirements of high second-harmonic generation(SHG) response,wide bandgap,and phase-matching capabilities.Herein,we propose a triplesite modulation strategy by synergistically tailoring the A-site cations(2-methylimidazole cation/1-ethyl-3-methylimidazole cation),B-site metals(Sn^(2+)/Pb^(2+)),and X-site halogens(Cl/Br),which effectively disrupts lattice symmetry and enables NCS crystallization.Our results demonstrate a strong SHG response,an expanded optical bandgap and increased birefringence.The optimized compound C_(6)H_(11)N_(2)PbCl_(3) exhibits a moderately strong SHG efficiency of 3.8 × KDP,a wide bandgap(3.87 eV),and enhanced birefringence(0.139@1064 nm),surpassing majority hybrid NLO materials.The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals,facilitating the integration of various aromatic heterocyclic cations.This research provides a robust strategic framework for the development of advanced NLO materials.
基金supported by the National Natural Science Foundation of China(21101090 and 21561021)。
文摘Three isostructural lanthanide complexes,namely[Ln(L)_(3)·CH_(3) OH](Ln=Tb(1),Dy(2),Ho(3),HL=N-(pyridin-2-ylcarbamothioyl)benzamide),were successfully synthesized and characterized by IR,UV,elemental analysis,single-crystal X-ray diffraction and DNA-biding analysis.X-ray single-crystal diffractions show that the family of lanthanide complexes crystallizes in monoclinic C2/c space group.Each lanthanide atom is coordinated with three carbonyl-O atoms,three pyridyl-N atoms and three imine-N atoms from three distinct L^(-1) ligands,forming a distorted tricapped trigonal prism.The binding properties of complexes with ct-DNA were studied by simulating the physiological environment of human body.The results suggest that compounds could bind with ct-DNA through interaction under a spontaneous process.
