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Syntheses, Structures and Properties of 3d-4f Heterometallic Coordination Polymers Based on Tetradentate Metalloligand and Lanthanoid Ions
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作者 Xingnan Guo Jun Qian +1 位作者 Qiang Zhou Chi Zhang 《Journal of Materials Science and Chemical Engineering》 2018年第4期163-179,共17页
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
关键词 Coordination Polymers {Sm2}/{Dy2} CLUSTERS metalloligand Crystal Structure Magnetic Property
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Synthesis and Characterization of Heterobimetallic Zigzag Chains with a Close-packed Structure Based on Macrocyclic Metalloligands
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作者 SHI Xiao-Ming XIAO Li-Na +1 位作者 LI Shu-Jing LI Xiao-Zeng 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2020年第8期1465-1474,1359,共11页
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
关键词 zigzag chain HETEROBIMETALLIC metalloligand crystal structure FLUORESCENCE
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一维配位聚合物{HgBr_2[μ_2-Cu(C_(26)H_(22)O_2N_4)]}n的合成与晶体结构
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作者 尚静 倪青玲 +4 位作者 桂柳成 王修建 黄廷洪 马凯 曾建强 《广西师范大学学报(自然科学版)》 CAS 北大核心 2011年第2期61-64,共4页
金属有机配体[Cu(L)2](L-=2-(3-吡啶甲基亚胺甲基)苯酚基)作为构筑单元与HgB r2反应,合成了一维配位聚合物{HgB r2[μ2-Cu(C26H22O2N4)]}n。X-射线单晶结构分析表明该配合物为单斜晶系,空间群为C 2/c,晶胞参数为:a=2.814 49(13)nm,b=0.6... 金属有机配体[Cu(L)2](L-=2-(3-吡啶甲基亚胺甲基)苯酚基)作为构筑单元与HgB r2反应,合成了一维配位聚合物{HgB r2[μ2-Cu(C26H22O2N4)]}n。X-射线单晶结构分析表明该配合物为单斜晶系,空间群为C 2/c,晶胞参数为:a=2.814 49(13)nm,b=0.624 53(3)nm,c=1.564 47(6)nm;β=114.808(4)°。Cu2+与来自2个配阴离子L-中的酚氧原子和亚胺氮原子反式配位形成一个中心对称[CuL2]基元,该基元中Cu2+的几何构型为平面四边形。每个[CuL2]基元以未配位的吡啶基团桥连相邻的HgB r2构筑成一维无限链。Hg2+由2个氮原子和2个B r-配位形成扭曲的四面体几何构型。链与链之间通过π…π作用形成二维超分子结构。 展开更多
关键词 金属有机配体 构筑单元 合成 晶体结构
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Engineering Heteronuclear Arrays from Ir^(Ⅲ)-Metalloligand and Co^(Ⅱ)Showing Coexistence of Slow Magnetization Relaxation and Photoluminescence 被引量:1
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作者 Kun Fan Song-Song Bao +4 位作者 Zi-Wen Yu Xin-Da Huang Yu-Jie Liu Mohamedallly Kurmoo Li-Min Zheng 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2022年第8期931-938,共8页
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
关键词 Crystal engineering Heterometallic complexes Iridium(Ⅲ)metalloligand Slow magnetization relaxation LUMINESCENCE
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An iridium(Ⅲ)-palladium(Ⅱ) metal-organic cage for efficient mitochondria-targeted photodynamic therapy 被引量:1
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作者 Chaojie Li Yaping Wang +6 位作者 Yulin Lu Jing Guo Chengyi Zhu Haozhe He Xiaohui Duan Mei Pan Chengyong Su 《Chinese Chemical Letters》 SCIE CAS CSCD 2020年第5期1183-1187,共5页
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
关键词 Metal-organic cage Photodynamic therapy Mitochondria-targeted Ir(Ⅲ)metalloligand Two-photon
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三个新大环草酰胺Ni(Ⅱ)配合物配体的合成、结构和DNA切割活性研究 被引量:1
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作者 丁贝贝 李尚浩 +3 位作者 马志刚 郝鹏鹏 李孝增 朱莉娜 《南开大学学报(自然科学版)》 CAS CSCD 北大核心 2013年第3期1-9,共9页
合成了3个新的大环草酰胺Ni(Ⅱ)单核配合物NiL1(1),NiL2·CH3CH2OH(2)和NiL3·1.25H2O(3).由于羟基和草酰胺基团的氧原子都能够与金属离子配位,因此,NiL1-3可以用作构筑同多核和异多核配位化合物的配合物配体.X-... 合成了3个新的大环草酰胺Ni(Ⅱ)单核配合物NiL1(1),NiL2·CH3CH2OH(2)和NiL3·1.25H2O(3).由于羟基和草酰胺基团的氧原子都能够与金属离子配位,因此,NiL1-3可以用作构筑同多核和异多核配位化合物的配合物配体.X-射线单晶结构分析表明,每个大环配体的4个N原子与Ni(Ⅱ)配位,构成变形的平面正方形配位环境;Ni—N键的长度都非常短,表明3个大环配体中所有氮原子的配位能力都很强.1~3中的醇羟基使羟自由基淬灭,从而抑制了配合物切割DNA的活性. 展开更多
关键词 晶体结构 大环配合物 金属配合物配体
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基于多吡啶Ru(Ⅱ)金属配体的Pd4Ru8型金属-有机分子笼的组装与性能研究
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作者 李超捷 刘媛媛 +2 位作者 王亚平 郭靖 潘梅 《中国科学:化学》 CAS CSCD 北大核心 2020年第6期687-694,共8页
本文以Ru(Ⅱ)的多吡啶金属配合物[Ru(bpy)2(qpy)(BF4)2](qpy=4,4′:2′,2′′:4′′,4′′′-四吡啶,bpy=2,2′-联吡啶)作为金属配体与平面四配位的Pd^2+进行二次配位自组装,得到一例较为罕见的Pd4Ru8型金属-有机分子笼racMOC-52.通过X... 本文以Ru(Ⅱ)的多吡啶金属配合物[Ru(bpy)2(qpy)(BF4)2](qpy=4,4′:2′,2′′:4′′,4′′′-四吡啶,bpy=2,2′-联吡啶)作为金属配体与平面四配位的Pd^2+进行二次配位自组装,得到一例较为罕见的Pd4Ru8型金属-有机分子笼racMOC-52.通过X射线单晶衍射确定了分子笼的空间结构,发现该类分子笼为缺上下底面的、类似柱状的立方体结构.进一步通过诱导预拆分方法,得到了纯手性的Δ/Λ-[Ru(bpy)2]^2+,并将其作为前驱体,再通过分步组装策略,成功得到了纯手性的Δ/Λ-Ruqpy金属配体和Δ/Λ-MOC-52金属-有机分子笼.探究了分子笼的单光子、双光子发光和对客体分子四苯硼钠的发光增强特性,以及单一手性分子笼的圆二色和圆偏振发光等性能. 展开更多
关键词 金属-有机分子笼 多吡啶金属配体 单一手性 圆偏振发光
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