酚氧桥联的不对称双铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成和磁性

本文合成了一组新的不对称双核配合物「Cu(samen)Cu(terp)」和「Cu(samen)Zn(terp)」,samen~4和terp分别表示N N’-乙二水杨酰胺胺根阴离子和2.2′:6′2″-联三吡啶。配合物「Cu(samen)Cu(terp)」的变温磁化率已测,其数值用最小二乘法与Bleancy-Bowers方程拟合,求得交换积分J=-0.538cm~(-1),表明配合物中铜离子间有极弱的反铁磁自旋交换作用。     

Aggregate manganese Schiff base moieties by terephthalate or acetate: dinuclear manganese and trinuclear mixed metal Mn2/Na complexes

A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.     

四溴代邻苯二甲酸根桥联的双核钴（Ⅱ）配合物的合成和表征

合成和表征了４种以四溴代邻苯二甲酸根阴离子（４Ｂｒ－ＰＨＴＨ）桥联、以１，１０－菲咯啉（ｐｈｅｎ），５－硝基－１，１０－菲咯啉（ＮＯ_２－ｐｈｅｎ），２，２′－联吡啶（ｂｐｙ）和４，４′－二甲基－２，２′－联吡啶（Ｍｅ_２ｂｐｙ）端接的双核钴（Ⅱ）配合物［Ｃｏ_２（４Ｂｒ－ＰＨＴＨ）（Ｌ）_４］（ＣｌＯ_４）（Ｌ＝ｐｈｅｎ（ｌ），ＮＯ_２－ｐｈｅｎ（２），ｂｐｙ（３），Ｍｅ_２ｂｐｙ（４））。基于ＩＲ光谱、元素分析、电导测量等方法推定配合物具有四溴代邻苯二甲酸根桥联结构和Ｃｏ（Ⅱ）离子具有畸变的八面体配位环境。进行了配合物变温磁化率（７５～３００Ｋ）的测定，其数据已用从自旋哈密顿符导出的磁方程拟合，求得交换参数Ｊ＝－０．８７ｃｍ~（－１）（１），－０．８４ｃｍ~（－１）（２），－０．８２ｃｍ~（－１）（３），－０．８５ｃｍ~（－１）（４），表明金属离子间有弱的反铁磁性自旋交换相互作用。     

Synthesis and properties of one-dimensional Ni(Ⅱ) and Ni(Ⅱ)Cu(Ⅱ) complexes linked by hydrogen bond

Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.     

Synthesis,crystal structure and magnetic properties of a novel manganese(II)-nitronyl nitroxide-azido(μ<Subscript>1,1</Subscript> and μ<Subscript>1,3</Subscript>) one-dimensional complex

A novel one-dimensional manganese(II) complex containing nitronyl nitroxide radical [Mn₂(IM2-py)₂(Ac)₂(μ_1,1-N₃)(μ_1,3-N₃) · EtOH] _n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p2₁/n. Each Mn(II) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(II) ions are linked by nitrogen atom of μ_1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through μ_1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds, π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(II) ion, weak antiferromagnetic interactions between the Mn-R units, and very weak antiferromagnetic interactions between the R-Mn-Mn-R units.     

Two-Dimensional Supramolecular from the Self-Assembly of Dissymmetrical Oxamidato-Bridged Heterometallic Trinuclear Building Blocks: Synthesis, Crystal Structure, and Magnetic Properties

Two heterometallic trinuclear complexes {[Cu(oxbp)]₂Co(H₂O)₂}1.5DMF0.5H₂O (complex 1) and {[Cu(oxbm)]₂Co(H₂O)₂}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]^– and [Cu(oxbm)]^–[H₃oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H₃oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm^–1 for complex 1 and 2, respectively.     

Synthesis, crystal structure and magnetic properties of a novel manganese(II)-nitronyl nitroxide-azido(μ_(1,1) and μ_(1,3)) one-dimensional complex

A novel one-dimensional manganese(Ⅱ) complex containing nitronyl nitroxide radical [Mn2(IM2-py)2(Ac)2((μ1.1-N3)(μ1,3-N3) . EtOH]n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p21/n. Each Mn(Ⅱ) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(Ⅱ) ions are linked by nitrogen atom of μ1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through u1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds,π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(Ⅱ) ion, weak antiferromagnetic inter     

Hetero‐tri‐spin [2p‐3d‐4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo‐Ligands: Synthesis,Structure, and Magnetic Properties

Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln₃Cu(hfac)₁₁(NitPhOAll)₄] (Ln^III=Gd 1_Gd , Tb 1_Tb , Dy 1_Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln₃Cu(hfac)₁₁(NitPhOPr)₄] (Ln^III=Gd 2_Gd , Tb 2_Tb , Dy 2_Dy , Ho 2_Ho , Yb 2_Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln₃Cu(hfac)₁₁(NitPhOBz)₄] (Ln^III=Gd 3_Gd , Tb 3_Tb , Dy 3_Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1_Tb and 2_Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior.     

四碘代对苯二甲酸根桥联的双钴(II)配合物的研究

报导了四种新的双核钴（Ⅱ）配合物，即［Co2（4I-TPHA）（L）4］（COl4）（4I-TPHA＝四碘代对苯二甲酸根阴离子，L＝1，10菲咯啉（phen）（1），5-硝基-,10菲咯啉（NO2-phen）（2），2，2′-联吡啶（bpy）（3）和4，4′-二甲基-2，2′-联吡啶（Me2bpy）（4）的合成和表征，配合物的磁性研究表明双核钴（Ⅱ）离子间有弱的反铁磁性自旋交换相互作用。     

Synthesis,Characterizations, Magnetism and Thermal Degradation of a 2‐Fold Interpenetrated 3D Cobalt‐Organic Framework

A new coordination polymer, [Co₂(L)₂(4,4′‐bipy)]_n·3nH₂O ( 1 ) based on 5‐(3‐methyl‐5‐phenyl‐4H‐1,2,4‐triazol‐4‐yl)isophthalic acid (H₂ L ) and 4,4′‐bipyridine (4,4′‐bipy) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, XRPD, IR, and elemental analysis. Temperature‐dependent magnetic susceptibility and thermal degradation for 1 were also studied. The asymmetric unit of compound 1 consists of two crystallographically independent Co(II) ion, two L ^2? ligand, one 4,4′‐bipy ligand, and three lattice water molecules. The 2D triangle networks were linked by the bridging 4,4′‐bipy ligand to give rise to a 2‐fold interpenetrated 3D architecture. The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II) cations and three L ^2? ligands. So we can define Co(II) ions as 4‐connected nodes and the L ^2? ligands as 3‐connected nodes. Thus, the 3D structure can be described as a 2‐fold parallel interpenetrated ins InS 3,4‐conn topology.