Syntheses,Crystal Structures and Magnetic Properties of Two Lanthanide Mononuclear Complexes

Two isostructural lanthanide complexes, [Tb(salen)_2]_3·3C_2H_9N_2·4CH_4O(1) and [Er(salen)_2]_3·3C_2H_9N_2·2CH_4O(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 salen2-ligands, forming distorted square antiprism geometry. Both 1 and 2 exhibit obvious slow magnetization relaxation under an applied 2 k Oe magnetic field.     

Syntheses,Structures, and Magnetic Properties of Two DMTCNQ and DETCNQ Gadolinium Complexes

Two DMTCNQ (DMTCNQ = 2,5‐dimethyl‐7,7,8,8‐tetracyano‐p‐quinodimethane) and DETCNQ (DETCNQ = 2,5‐diethyl‐7,7,8,8‐tetracyano‐p‐quinodimethane) gadolinium complexes [Gd(DMTCNQ)₂(CH₃OH)(H₂O)₆][DMTCNQ] · 4H₂O ( 1 ) and [Gd(DETCNQ)(H₂O)₇][2DETCNQ] ( 2 ) were synthesized by reactions of GdCl₃ · 6H₂O with Li(DMTCNQ) or Li(DETCNQ). X‐ray diffraction analysis reveals that complexes 1 and 2 are discrete complexes. The central metal atom in 1 is coordinated by two DMTCNQ ligand radicals whereas that in 2 is coordinated by just one DETCNQ ligand radical. The adjacent molecules are connected by the intermolecular hydrogen bonds to form the two‐dimensional (2D) supramolecular layer structures, which are further packed into a three‐dimensional (3D) supramolecular architecture through the π–π interactions between ligand radicals in 1 and 2 . Magnetic investigation indicates that the antiferromagnetic interactions between spin carriers exists in 1 and 2 .     

两个双核稀土金属配位聚合物的溶剂热合成、晶体结构及荧光性质

以顺丁烯二酰肼(MH)为配体,通过溶剂热法合成了配位聚合物[Dy2(MH)6]n·0.5DMF(1)和[Eu2(MH)6]n(2)。通过红外光谱、X射线粉末衍射、X射线单晶衍射表征了2个晶体的结构。配合物1和2都是三斜晶系,P1空间群。以双核结构为顶点作图得到配合物的空间拓扑结构,拓扑类型为tsi。配合物的热重分析结果表明2个配合物在315℃左右仍有较好的热稳定性。固体荧光结果表明配合物2在激发波长为375 nm时有对应Eu~(3+)的5D0→7FJ(J=0~4)能级能量的5个发射峰,最强发射峰波长为616 nm,归属为Eu~(3+)的5D0→7F2能级跃迁。     

两个双核稀土金属配位聚合物的溶剂热合成、晶体结构及荧光性质

以顺丁烯二酰肼（MH）为配体,通过溶剂热法合成了配位聚合物[Dy₂（MH）₆]_n·0.5DMF（1）和[Eu₂（MH）₆]_n（2）。通过红外光谱、X射线粉末衍射、X射线单晶衍射表征了2个晶体的结构。配合物1和2都是三斜晶系,P1空间群。以双核结构为顶点作图得到配合物的空间拓扑结构,拓扑类型为tsi。配合物的热重分析结果表明2个配合物在315℃左右仍有较好的热稳定性。固体荧光结果表明配合物2在激发波长为375 nm时有对应Eu³⁺的⁵D₀→⁷F_J（J=0~4）能级能量的5个发射峰,最强发射峰波长为616 nm,归属为Eu³⁺的⁵D₀→⁷F₂能级跃迁。     

Two Isostructural Layered Lanthanide(III) Complexes: Syntheses,Structures, Magnetic and Luminescent Properties

Two N'-(2-hydroxybenzylidene)pyridine N-oxide-carbohydrazide (H₃L)-based coordination complexes with the formula [Ln₂(DMF)₂(OAc)₂(HL)₂]_n (Ln = Dy for 1 and Eu for 2 ) were solvothermally synthesized. Crystal structures, thermal stabilities, magnetic and luminescent properties of the two complexes were fully investigated. Both complexes are isomorphic two-dimensional layers with centrosymmetric {Ln₂} subunits extended by doubly deprotonated HL^2– connectors. Complex 1 with highly anisotropic Dy^III spin exhibits slightly frequency-dependent magnetic relaxations under zero dc field with an effective energy barrier of ca. 6.84 K. Eu^III-based complex 2 displays only one weak fluorescent emission around 532 nm with the absence of characteristic emission of Eu^III ion. These results provide helpful hints of the hydrazide Schiff-functionalized organic ligands on the function modulations of the resulting Ln complexes.     

Syntheses,Crystal Structures and Magnetic Properties of Two Nitrophenyl Substituted Nitronyl Nitroxide Radical-lanthanide Complexes

Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln(hfac)3(NITmNO_2)2](Ln = Sm(ⅡI)(1), Tb(ⅡI)(2), hfac = hexafluoroacetylacetonate, NITmNO_2 = 2-(3-nitrophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln(ⅡI)-radical structures, in which the central Ln(ⅡI) ions are all eight coordinated in D2 d dodecahedral(DD) geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm(ⅡI) ion and NITmNO_2 in complex 1, while weak ferromagnetic interaction between Tb(ⅡI) ion and NITmNO_2 in complex 2.     

席夫碱类混价七核锰金属配合物的合成、表征及磁性

以3-乙氧基水杨醛缩乙醇胺席夫碱(H2L)为配体合成了2个新的七核锰配合物[Na2MnⅡMnⅢ6O2(L)6(N3)4(CH3COO)2]·4DMF(1)和[Na2MnⅡMnⅢ6O2(L)6(SCN)4(CH3COO)2]·2DMF (2),并对它们进行红外分析、元素分析、热重分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为混价七核锰配合物,包含1个Mn2+和6个Mn3+。此外还研究了配合物1和2的磁学性质,磁性研究表明配合物1和2都表现出反铁磁作用。     

Two New Coordination Complexes Based on Eosin Y Dye Ligand:Syntheses,Crystal Structures and Magnetic Properties

Two novel coordination compounds formulated as [Co_2(EY)_2(L_1)]·2C_2H_5OH(1) and [Mn_2(EY)_2(L_1)]·2C_2H_5OH(2)(EY = Eosin Y dianion, L_1 = 4,4'-bipyridine) based on Eosin Y dye ligand have been prepared by solvothermal reactions and structurally characterized. Single-crystal X-ray diffraction studies reveal that compounds 1 and 2 are isostructural. They show weak antiferromagnetic coupling between the adjacent Co~Ⅱ and Mn~Ⅱ ions, respectively.     

两个三维柱层式单一手性配位化合物:合成、结构和性质（英文）

在溶剂热合成条件下得到2个单一手性配位聚合物,即[Cd3((R)-CIA)2(bipy)2.5(H2O)2]·xGuest(1)和[Zn3((R)-CIA)(bmib)2(H2O)2 Cl]·H2O·xGuest(2)((R)-H3CIA=(R)-5-(1-羧基乙氧基)间苯二甲酸,bipy=4,4′-联吡啶,bmib=1,4-双(2-甲基-1H-咪唑-1-基)苯)。X射线单晶结构分析揭示配合物1和2都是柱层式结构的三维框架。从拓扑分析的角度看,配位物1具有(3,3,3,6,6)-连接的网络,拓扑符号为(4.5^2)2(4.8^2)2(42.6^8.8^3.10^2)(4^2.6^8.8^3.9^2)(5.8.9)2,而配合物2是(3,4,4)-连接的网络,拓扑符号为(6·7^2)2(6·7^5)2(6^2·7^4)。此外,对上述配合物的热稳定性、圆二色谱和荧光性质也做了研究。     

Polynuclear Complexes with Alkoxo and Phenoxo Bridges from In Situ Generated Hydroxy‐Rich Schiff Base Ligands: Syntheses,Structures, and Magnetic Properties

Complexes of new Schiff base ligands generated in situ from the reaction of 1‐aminoglycerol, aldehydes, and metal ions are reported. [Cu₄(HL¹)₄] ( 1 ) and [Ni₄O(HL¹)₃(H₂O)₃)] ? 6 H₂O ? DMF ? DMSO ( 2 ) have M₄O₄ cubane cores, with the L/M molar ratios of 4:4 and 3:4, respectively. [Mn^III₃Mn^IINaOCl₄(HL¹)₃] ? 3 M eCN ( 3 ) has a unique pentanuclear trigonal propeller‐shaped Mn^III₃Mn^IINa core structure, and the coordination assemblies are linked by hydrogen bonds to afford a 3D channel structure. [Cu₂(HL²)₂] ( 4 ) has a bis(μ₂‐alkoxo)‐bridged Cu₂O₂ core, with the binuclear species linked by hydrogen bonds to afford a 1D double‐chain. [Ni₇(OH)₂(OCH₃)₄(H₂L³)₂(MeOH)₂(H₂O)₂]‐ (ClO₄)₂ ? 10 H₂O ( 5 ) has a heptanuclear structure containing heptadentate di‐Schiff base ligands, with the nickel(II) ions bridged by phenoxo, alkoxo, hydroxo, and methoxo groups to afford a very rare face‐sharing hexadruple defective cubane core with a Ni@Ni₆ arrangement. The lattice water molecules are linked by hydrogen bonds to form helical chains, which are further hydrogen‐bonded to the coordination moieties to afford a 2D network. Variable temperature magnetic susceptibility measurements and nonlinear data‐fitting revealed that the “2+4” type of cubane complex 1 shows medium intradimeric ferromagnetic interactions and weak interdimeric ferromagnetic interactions. For complexes 2 and 5 , coexistent ferro‐ and antiferromagnetic couplings afford a non‐zero spin ground state. However, compound 3 shows antiferromagnetic interactions between Mn^III and Mn^II, and ferromagnetic interactions between the Mn^III centers, resulting in a global antiferromagnetic behavior. In conclusion, the reaction of 1‐aminoglycerol with aldehydes and metal salts afforded polynuclear complexes with a rich structural diversity and remarkable magnetic behavior.     

席夫碱类三明治型铽/镝金属配合物的合成、表征及磁性

以N,N′-二(4-甲氧基水杨基)邻苯二胺(H2L)为配体合成了2个新的稀土配合物[M_2L_3(H_2O)](M=Tb (1),Dy (2)),并对它们进行了红外分析、元素分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为三明治型双核配合物。此外还研究了配合物1和2的磁学性质,结果表明配合物1和2都表现出反铁磁性作用和场诱导效应引起的慢弛豫行为。配合物2的有效能垒和驰豫时间分别为35.45 cm-1和2.7×10~(-10) s。     

两个双核稀土-自由基化合物的合成、结构及磁性

以乙酰丙酮为共配体的稀土配合物与2-羟基苯取代的自由基配体进行反应得到2个新颖的稀土-自由基配合物[Ln₂（acac）₄（NIT-PhO）₂]（Ln=Tb（1）,Y（2）;acac=乙酰丙酮,NIT-PhOH=2-（2''-hydroxyphenyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide）。2个配合物的结构相同,均是通过2个自由基配体上的羟基氧原子桥联2个稀土离子构成双核结构。直流磁化率的研究表明配合物2具有弱的反铁磁性质。     

Syntheses,Crystal Structures and Luminescent Properties of Two Schiff Base Complexes

Two new transition metal complexes based on chiral Schiff base ligand, namely Zn(L_1)_2(1) and Cd(L_2)2(2)(L 1=(R,E)-3-(2-hydroxy-3-methoxybenzylideneamino)propane-1,2-diol, L2=(R,E)-2-((2-hydroxy-1-phenylethylimino)methyl)-6-methoxyphenol), have been synthesized and characterized. Single-crystal X-ray diffractions reveal that both 1 and 2 crystallize in the same monoclinic space group C_2. 1 is four-coordinated, while 2 is six-coordinated. Complexes 1 and 2 show fluorescent emission at 479 and 580 nm, respectively. Moreover, 1 and 2 exhibit selective and sensitive recognition toward Zn~(2+)/Cd~(2+) ions in the methanol solution.     

基于半胱氨酸衍生物的两个手性多核金属簇合物的结构和磁性质

采用具有手性的半胱氨酸衍生物配体L-硫代脯氨酸(LTP)分别和高氯酸钴、高氯酸锰反应得到配合物[Co(LTP)₂]_n(1)和[Mn(LTP)₂]_n(2)。用X-射线衍射对这2个化合物的晶体结构进行了测定,结果表明4个LTP配体采用μ₂-N₁O₂:O₃的配位模式将八面体配位构型的金属离子连接起来构成二维结构。磁性测定表明2个化合物中金属离子之间有弱的反铁磁相互耦合作用。     

Three Phenoxo‐Bridged Dinuclear Lanthanide Complexes: Syntheses,Crystal Structures,and Magnetic Properties

Three dinuclear lanthanide complexes [Ln₂(H₂L)₂(NO₃)₄] [Ln = Dy ( 1 ), Tb ( 2 ), and Gd ( 3 )] [H₃L = 2‐hydroxyimino‐N′‐[(2‐hydroxy‐3‐methoxyphenyl)methylidene]‐propanohydrazone] were solvothermally synthesized by varying differently anisotropic rare earth ions. Single‐crystal structural analyses demonstrate that all the three complexes are crystallographically isostructural with two centrosymmetric Ln^III ions aggregated by a pair of monodeprotonated H₂L^– anions. Weak intramolecular antiferromagnetic interactions with different strength were mediated by a pair of phenoxo bridges due to superexchange and/or single‐ion anisotropy. Additionally, the Dy^III‐based entity shows the strongest anisotropy exhibits field‐induced single‐molecule magnetic behavior with two thermally activated relaxation processes. In contrast, 3 with isotropic Gd^III ion has a significant cryogenic magnetocaloric effect with the maximum entropy change of 25.7 J · kg^–1 · K^–1 at 2.0 K and 70.0 kOe.     

Room Temperature Syntheses,Structures and Magnetic Properties of Two Heterometallic Tetranuclear Clusters

Two new heterometallic tetranuclear clusters [M₂Na₂(hmb)₄(N₃)₂(CH₃CN)₂]·(CH₃CN)₂ (M = Ni (1), M = Co (2), Hhmb is 2-hydroxy-3-methoxy-benzaldehyde) have been synthesized at room temperature and structurally characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. Intracluster, compounds 1 and 2 display dominant ferromagnetic interaction through double μ _1,1,1-N₃ bridges, while intercluster, 1 and 2 display weak anti-ferromagnetic interaction and ferromagnetic interaction, respectively.     

Syntheses,Structures, and Properties of Two Coordination Complexes of a Flexible Ligand with Channel Structure

Two complexes of 3,5‐bis(4‐carboxyphenylmethyloxy) benzoic acid (H₃L) and transition metal ions, [Zn₂(μ₃‐OH)(L)] · H₂O ( 1 ) and (H₃O)[Cu₂(μ₄‐O)(L)] · H₂O ( 2 ) were synthesized under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction and further characterized by elemental analysis, IR and diffusion UV/Vis/NIR spectroscopy, and TGA. The complexes possess 3D open frameworks with different shapes (rhombus / square) and sizes of channels resulting from the trans/cis‐configurations and coordination modes (μ₈‐η¹:η¹:η¹:η²:η¹:η² for 1 and μ₆‐η¹:η¹:η¹:η¹:η¹:η¹ for 2 ) of the flexible ligand and the property of transition metal ions. In addition, photoluminescence spectra of 1 and 2 were also discussed. In 2 there exists antiferromagnetic interaction showing that μ₄‐O atom in {Cu₂O}_n chain does not favor the magnetic exchange between Cu²⁺ ions.     

两种有机磺酸配合物的合成、表征及与DNA键合性质

合成了2个新型有机磺酸配合物,[Cd(phen)₂(ans)₂]·H₂O (1)和[Pb(phen)₂(ans)₂]·H₂O (2) (phen=1,10-邻菲咯啉,ans=4-氨基-1-萘磺酸根),通过元素分析、红外光谱等对配合物进了表征,用X-射线单晶衍射方法测定了配合物的单晶结构。应用紫外-可见吸收光谱、荧光光谱及粘度测定方法研究了配合物与ctDNA的作用,发现2个配合物均以插入和氢键两种模式与ctDNA发生作用。     

两个一维之字链异三金属配位聚合物的合成、结构和磁性

用分步合成法得到了2个结构新颖的一维之字链异三金属配位聚合物{[Cu(Me_2valpn)Dy(DMF)_2(H_2O)Fe(CN)_6]·1.5H_2O·0.5CH_3OH}n(1)和{[Cu(Me_2valpn)Tb(DMF)_2(H_2O)Fe(CN)_6]·H_2O·CH_3OH}n(2)(H_2Me_2valpn=N,N′-双(3-甲氧基-水杨醛)缩-2,2-二甲基-1,3-丙二胺)。X射线单晶衍射分析表明每个[Fe(CN)_6]3-用顺式的2个氰根分别连接2个相邻构筑单元[Cu(Me_2valpn)Ln(DMF)_2(H_2O)]_3+的Cu(Ⅱ)和Ln(Ⅲ)。除了Cu(Ⅱ)和Ln(Ⅲ)之间的双酚氧桥之外,链中还包含Fe-C≡N-Cu和Fe-C≡N-Ln两类弯曲的桥联结构。配合物1在9.5~300 K的直流变温磁化率数据符合居里-韦斯定律,韦斯常数(θ)为13.17 K,表明配合物1总体上表现铁磁相互作用。交流磁化率测试表明配合物1没有表现出缓慢磁弛豫现象。