Based on tetradentate metalloligand LCu ([Cu(2,4-pydca)2], 2,4-pydca = pyridine-2,4-dicarboxylate) and lanthanides (Sm3+, Dy3+), two 3d-4fheterometalliccoordination polymers, namely, {[Sm2 (DMSO)4 (CH3OH) 2][LCu]3...Based on tetradentate metalloligand LCu ([Cu(2,4-pydca)2], 2,4-pydca = pyridine-2,4-dicarboxylate) and lanthanides (Sm3+, Dy3+), two 3d-4fheterometalliccoordination polymers, namely, {[Sm2 (DMSO)4 (CH3OH) 2][LCu]3·7DMSO·2CH3OH}n 1 and {[Dy2 (DMSO)3 (CH3OH)][LCu3 (DMSO)]·4DMSO·CH3OH}n 2 (DMSO = dimethyl sulfoxide), have been synthesized and well characterized by elemental analysis, Fourier-transform infrared spectroscopy, thermogravimetric and single-crystal X-ray diffraction analysis. Single-crystal X-ray analysis reveals that both 1 and 2 crystallize in the triclinic crystal system with P-1 space group and possess the 3D framework structures, which are constructed from metalloligands LCu connecting with {Sm2} and {Dy2} clusters, respectively. The 3D structure of 1 has a 6-connected single-nodal topology with the point symbol {49 × 66}, while 2 features a different framework with the point symbol of {412 × 63}. Thermogravimetric analysis exhibits that the skeleton of both 1 and 2 collapse after 350℃. Magnetic properties of 1 and 2 have also been investigated.展开更多
Two new heterobimetallic coordination polymers{[Co(NiL)(H2O)3]·4H2O}n(1)and{[Cu(NiL)(H2O)3]·4H2O}n(2)were synthesized based on metalloligand under the same self-assembly conditions.X-ray diffraction analyses...Two new heterobimetallic coordination polymers{[Co(NiL)(H2O)3]·4H2O}n(1)and{[Cu(NiL)(H2O)3]·4H2O}n(2)were synthesized based on metalloligand under the same self-assembly conditions.X-ray diffraction analyses reveal that the two compounds involve close-packed zigzag chains,which expand into various three-dimensional supramolecular frameworks through the second interactions such as hydrogen bonds andπ···πstacking interactions.In these two compounds,NiL as a bridging ligand chelates the metal ion nodes via two oxamido carbonyls and carboxylate oxygen atom.The central Co(Ⅱ)and Cu(Ⅱ)ions in 1 and 2 both exhibit distorted octahedral coordination geometry.They are bridged by macrocyclic oxamido metalloligands fusing the zigzag chains with a‘‘head-to-tail’’arrangement.The Ni(Ⅱ)ion in metalloligand is coordinated by four nitrogen atoms with the[NiN4]chromophore exhibiting distorted planarity.The two investigated compounds were further characterized by thermogravimetric analysis and FT-IR spectroscopy.The fluorescent properties of 1 and 2 in the solid state were also investigated.展开更多
Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2...Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2·15H_(2)O(3)and{Co(H_(2)O)2[Ir(ppyCOO)_(2)(bpy)]_(2)}·2CH_(3)OH·3H_(2)O(4),have been synthe-sized by combining paramagnetic Co^(Ⅱ)ion with luminescent Ir^(Ⅲ)-metalloligand,[Ir(ppyCOOH)_(2)(bpy)][Ir(ppyCOO)_(2)(bpy)]·5H_(2)O(1),where ppyCOOH=3-(pyridin-2-yl)benzoic acid and bpy=2,2'-bipyridyl.Owing to the variable charged states of compound 1 at dif-ferent pH,compounds 2 and 3 are discrete ionic complexes containing hydrated Co^(2+)cations and deprotonated[Ir(ppyCOO)_(2)(bpy)]-anions as well as coexisting neutral[Ir(ppyCOO)(ppyCOOH)(bpy)](for 2)or Co(H_(2)O)_(4)[Ir(ppyCOO)_(2)(bpy)]_(2) trinuclear molecule(for 3).Whereas compound 4 consists of self-assembled two-dimensional coordination polymer with Co-metalloligand dative bonds.The hexa-coordinated Co^(Ⅱ)cores in all complexes display octahedral geometries with varying degrees of distortion.In a bias dc field,the ac susceptibilities for 2-4 reveal slow magnetic relaxation.Moreover,the solid-state phosphorescence is observed for compounds 2 and 3 due to weak supramolecular interaction between Co^(Ⅱ)ion and Ir-moiety but is severely quenched for 4,where the Co center is strongly connected to the metalloligand.To the best of our knowledge,this is the first report of Ir-Co systems showing both slow magnetization relaxation and photoluminescence.展开更多
An Ir8 Pd4-heteronuclear metal-organic cage(MOC-51)was assembled from bipodal metalloligand[Ir(ppy)2(qpy)(BF4)](qpy=4,4′:2′,2″:4″,4′′′-quaterpyridine;ppy-2-phenylpridine)with Pd(Ⅱ)salt.The cubic barrel shaped ...An Ir8 Pd4-heteronuclear metal-organic cage(MOC-51)was assembled from bipodal metalloligand[Ir(ppy)2(qpy)(BF4)](qpy=4,4′:2′,2″:4″,4′′′-quaterpyridine;ppy-2-phenylpridine)with Pd(Ⅱ)salt.The cubic barrel shaped MOC shows one-photon and two-photon excited deep-red emission,as well as large singlet oxygen quantum yields under visible light irradiation,therefore exhibiting great potentials in organelles-targeted cell imaging and photodynamic therapy(PDT).Compared with the Ir(Ⅲ)metalloligand,the Ir8 Pd4-MOC showed less dark toxicity and higher mitochondria-targeting efficiency.The localization in mitochondria overco mes the limitation of short lifetime and diffusion distance of ROS in cell,thus improved PDT effect can be obtained in low light dose usage of the MOC.This study presents the first case of Ir-based metal-organic cages for bio-applications in successful integration of imaging diagnosis and photodynamic therapy.展开更多
文摘Based on tetradentate metalloligand LCu ([Cu(2,4-pydca)2], 2,4-pydca = pyridine-2,4-dicarboxylate) and lanthanides (Sm3+, Dy3+), two 3d-4fheterometalliccoordination polymers, namely, {[Sm2 (DMSO)4 (CH3OH) 2][LCu]3·7DMSO·2CH3OH}n 1 and {[Dy2 (DMSO)3 (CH3OH)][LCu3 (DMSO)]·4DMSO·CH3OH}n 2 (DMSO = dimethyl sulfoxide), have been synthesized and well characterized by elemental analysis, Fourier-transform infrared spectroscopy, thermogravimetric and single-crystal X-ray diffraction analysis. Single-crystal X-ray analysis reveals that both 1 and 2 crystallize in the triclinic crystal system with P-1 space group and possess the 3D framework structures, which are constructed from metalloligands LCu connecting with {Sm2} and {Dy2} clusters, respectively. The 3D structure of 1 has a 6-connected single-nodal topology with the point symbol {49 × 66}, while 2 features a different framework with the point symbol of {412 × 63}. Thermogravimetric analysis exhibits that the skeleton of both 1 and 2 collapse after 350℃. Magnetic properties of 1 and 2 have also been investigated.
基金supported by the Natural Science Foundation of He’nan Educational Committee of China(17A150056)the National Natural Science Foundation of China(21501203)+2 种基金the Funds of Basic and Advanced Technology Research Project of Henan Province of China(192012310497)the Research Fund for the Doctoral Program of Higher Education of China(Zhoukou Normal University,No.ZKNUB2013003)the Funds of Zhoukou Normal University(ZKNUB115202)。
文摘Two new heterobimetallic coordination polymers{[Co(NiL)(H2O)3]·4H2O}n(1)and{[Cu(NiL)(H2O)3]·4H2O}n(2)were synthesized based on metalloligand under the same self-assembly conditions.X-ray diffraction analyses reveal that the two compounds involve close-packed zigzag chains,which expand into various three-dimensional supramolecular frameworks through the second interactions such as hydrogen bonds andπ···πstacking interactions.In these two compounds,NiL as a bridging ligand chelates the metal ion nodes via two oxamido carbonyls and carboxylate oxygen atom.The central Co(Ⅱ)and Cu(Ⅱ)ions in 1 and 2 both exhibit distorted octahedral coordination geometry.They are bridged by macrocyclic oxamido metalloligands fusing the zigzag chains with a‘‘head-to-tail’’arrangement.The Ni(Ⅱ)ion in metalloligand is coordinated by four nitrogen atoms with the[NiN4]chromophore exhibiting distorted planarity.The two investigated compounds were further characterized by thermogravimetric analysis and FT-IR spectroscopy.The fluorescent properties of 1 and 2 in the solid state were also investigated.
基金the National KeyR&D Program of china Nos 201YFA03032032018YFA0306004)the National Natural Science Foundation of China(No.21731003).
文摘Three heteronuclear Ir^(Ⅲ)-Co^(Ⅱ)arrays,[Co(H_(2)O)6]_(2)[Ir(ppyCOO)(ppyCOOH)(bpy)]_(2)[Ir(ppyCOO)_(2)(bpy)]_(2)(NO_(3))2·10.5H_(2)O(2),[Co(H_(2)O)6]{Co-(H_(2)O)4[Ir(ppyCOO)_(2)(bpy)]_(2)}[Ir(ppyCOO)_(2)(bpy)]2·15H_(2)O(3)and{Co(H_(2)O)2[Ir(ppyCOO)_(2)(bpy)]_(2)}·2CH_(3)OH·3H_(2)O(4),have been synthe-sized by combining paramagnetic Co^(Ⅱ)ion with luminescent Ir^(Ⅲ)-metalloligand,[Ir(ppyCOOH)_(2)(bpy)][Ir(ppyCOO)_(2)(bpy)]·5H_(2)O(1),where ppyCOOH=3-(pyridin-2-yl)benzoic acid and bpy=2,2'-bipyridyl.Owing to the variable charged states of compound 1 at dif-ferent pH,compounds 2 and 3 are discrete ionic complexes containing hydrated Co^(2+)cations and deprotonated[Ir(ppyCOO)_(2)(bpy)]-anions as well as coexisting neutral[Ir(ppyCOO)(ppyCOOH)(bpy)](for 2)or Co(H_(2)O)_(4)[Ir(ppyCOO)_(2)(bpy)]_(2) trinuclear molecule(for 3).Whereas compound 4 consists of self-assembled two-dimensional coordination polymer with Co-metalloligand dative bonds.The hexa-coordinated Co^(Ⅱ)cores in all complexes display octahedral geometries with varying degrees of distortion.In a bias dc field,the ac susceptibilities for 2-4 reveal slow magnetic relaxation.Moreover,the solid-state phosphorescence is observed for compounds 2 and 3 due to weak supramolecular interaction between Co^(Ⅱ)ion and Ir-moiety but is severely quenched for 4,where the Co center is strongly connected to the metalloligand.To the best of our knowledge,this is the first report of Ir-Co systems showing both slow magnetization relaxation and photoluminescence.
基金supported by the National Natrual Science Foundation of China(NSFC,Nos.21771197,21720102007,21821003)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01C161)FRF for the central universities。
文摘An Ir8 Pd4-heteronuclear metal-organic cage(MOC-51)was assembled from bipodal metalloligand[Ir(ppy)2(qpy)(BF4)](qpy=4,4′:2′,2″:4″,4′′′-quaterpyridine;ppy-2-phenylpridine)with Pd(Ⅱ)salt.The cubic barrel shaped MOC shows one-photon and two-photon excited deep-red emission,as well as large singlet oxygen quantum yields under visible light irradiation,therefore exhibiting great potentials in organelles-targeted cell imaging and photodynamic therapy(PDT).Compared with the Ir(Ⅲ)metalloligand,the Ir8 Pd4-MOC showed less dark toxicity and higher mitochondria-targeting efficiency.The localization in mitochondria overco mes the limitation of short lifetime and diffusion distance of ROS in cell,thus improved PDT effect can be obtained in low light dose usage of the MOC.This study presents the first case of Ir-based metal-organic cages for bio-applications in successful integration of imaging diagnosis and photodynamic therapy.