A Novel Macrocyclic Nickel(II) and Ferricyanide 1D Zigzag Chain: Synthesis,Crystal Structure,and Magnetic Properties

A novel cyan‐bridged macrocyclic nickel complex [{NiL¹}{Fe(bipy)(CN)₄}]2·5H₂O 1 (L¹ = 3,10‐dimethyl‐1,3,6,8,10,12‐hexaazacyclotetradecane, bipy = 2,2‐bipyridine) was synthesized and structurally characterized. The complex exhibits one‐dimensional zigzag chain structures. Each ferrous(II) ion connects two nickel(II) ions using two trans CN^? groups, and the remaining CN^? groups are terminal. Magnetic measurement shows weak ferromagnetic interaction between the nearest Ni(II) ions through the diamagnetic Fe(II) ion.     

一维链状锰配合物的合成、结构及磁性研究

合成了邻硝基苯磺酰化丙氨酸配体2-NBS-AlaH (1)(2-NBS-AlaH=邻硝基苯磺酰化丙氨酸)及其锰的配合物[Mn(4，4′-bipy)(H₂O)₄]₂[(4，4′-bipy)₂(H₂O)₃(2-NBS-Ala)₄] (2)。通过X-射线单晶衍射测定了其结构：配体通过氢键形成了一维链状结构；配合物2中，4，4′-bipy把锰离子连成了一维链状结构。磁性研究表明，配合物由于分子间的自旋耦合呈现出弱的铁磁性。     

Syntheses,Crystal Structures,and Magnetic Properties of Three 1D Chain Metal–Nitroxide Complexes Bridged by ­Flexible Dicarboxylate Anions

Three new one‐dimensional (1D) chain metal–nitroxide complexes {[Cu(NIT4Py)₂(suc)(H₂O)] · 3H₂O}_n ( 1 ), {[Cd(NIT4Py)₂(suc)(H₂O)] · [Cd(NIT4Py)₂(suc)(H₂O)₂] · 3H₂O}_n ( 2 ), and {[Zn(NIT4Py)(glu)(H₂O)] · H₂O}_n ( 3 ) [NIT4Py = 2‐(4′‐pyridyl)‐4, 4, 5, 5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide, suc = succinate anion and glu = glutarate anion] were synthesized and structurally characterized. Single‐crystal X‐ray analyses indicate that the three complexes crystallize in neutral 1D chains in which the metal‐nitroxide units are linked by flexible dicarboxylate anions. The succinate anions only adopt trans configuration in complexes 1 and 2 , whereas the glutarate anion has gauche/anti conformation in complex 3 . Magnetic measurements show that complex 1 exhibits weak antiferromagnetic interactions between the copper ions and the nitroxides.     

Synthesis,Structure and Luminescent Properties of Three 1D Chain Rare Earth Complexes

Three 1 D chain coordination polymers [Ln(pydc)2(H2 O)2]n·n Him(Ln = Dy(1), Gd(2), Sm(3), H2 pydc = pyridine-2,5-dicarboxylic acid, Im = imidazole), were solvothermally synthesized by the reaction of pyridine-2,5-dicarboxylic acid(H2 pydc), Ln(Ⅲ) salts and imidazole. They have been characterized by X-ray single-crystal diffraction, IR spectra, TGA analysis and elemental analysis. Structural analyses revealed that complexes 1～3 have similar 1 D chain structures and belong to P1 space group. It is noteworthy that complexes 1～3 exhibited excellent thermal stability and no weightlessness below 117 ℃. Meanwhile, 1 and 3 show characteristic fluorescence of corresponding lanthanide metal ions in solid state at room temperature.     

Copper Carboxylate-phosphonates: Syntheses,Crystal Structures and Magnetic Properties

Two novel copper carboxyly-phosphonates, namely, Cu_(2.5)(5-pnc)(SO_4)_(0.5)(OH)(H_2O)_(0.5)(1) and Cu_(0.5)(5-pncH_2)(H_2O)_(1.5)(2)(5-pncH_3 = 5-phosphono-1-naphthalenecarboxylic acid), have been synthesized and characterized by X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. In compound 1, each {PO_3C} tetrahedron is corner-shared with two {Cu(1)O_4}, two {Cu(2)O_5} and one {Cu(3)O_5},thus forming a one-dimensional inorganic chain along the c axis containing 8-membered rings of [Cu_3O_4S] and 19-membered cages of [Cu_5O_(10)P_4]. The inorganic chains are further connected by a 5-pnc~(3-) ligand to generate a three-dimensional framework. Compound 2 exhibits a one-dimensional structure, in which the inorganic chains of [Cu-O-Cu]_n are connected by the organic ligands through hydrogen bonding interactions, forming an infinite two-dimensional layer. Magnetic measurements of 1 indicate that dominant antiferromagnetic interactions are mediated between the Cu~(2+) centers.     

Syntheses,Structures and Fluorescent Properties of Two 1D Chain Organic Amines and Metal Iodine Organic-inorganic Hybrid Compounds

Two bifunctional amines, 4-(2-aminoethyl)morpholine and histamine, were heated with PbI_2 and BiI_3 in concentrated HI aqueous solution to give one-dimensional(1D) organicinorganic hybrid compounds [(C_6H_(16)N_2O)PbI4]n(1) and [(C_(16)H_(20)N_(20))Bi_2I_(10)](2), respectively. In 1, the [PbI6] octahedra formed double chain anions through sharing-corner and-edge, and the protonated(C_6H_(16)N_2O)~(2+) cations were located at the vicinity of the double chains by hydrogen bonds. In 2, the [BiI_6] octahedra firstly formed dimeric [Bi_2I_(10)]~(4-) anion through sharing edge, and subsequently, the protonated histamine cations worked as bridge to link alternately with [Bi_2I_(10)]~(4-) anion by hydrogen bonds to form organic-inorganic hybrid 1D chains. In addition, compound 1 emitted a green light at the excitation wavelength of 400 nm and the maximum emission wavelength is at 503 nm.     

Hydrogen-Bond Directed Cyanide-Bridged Supramolecular 2D and 1D Bimetallic Coordination Polymers: Synthesis,Crystal Structure,and Magnetic Properties

By using K₂[Ni(CN)₄] as a building block and two Mn(III) compounds containing bicompartimental Schiff-base ligands as assembling segments, two new cyanide-bridged Ni–Mn complexes of the formula {[Mn(L¹)(H₂O)]₄[Ni(CN)₄]}[ClO₄]₂·2CH₃CN (1) and {[Mn(L²)(H₂O)]₂[Ni(CN)₄]}·CH₃CN H₂O (2) (L¹ = N,N’-1,2-propylene-bis(3-methoxysalicylideneiminate; L² = N,N’-1,2-propylene-bis(3-ethoxysalicylideneiminate) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray analysis. Single Xray diffraction analysis revealed the cationic pentanuclear and neutral trinuclear structures for complexes 1 and 2, respectively, and indicated that the structure of the Schiff-base ligand had obvious influence on the structural types of the target cyanide-bridged complexes. Both cyanide-bridged complexes are self-complementary via coordinated aqua ligand from one complex and the free O₄ compartment from the neighboring complex, therefore giving supramolecular two-dimensional network and one-dimensional zig-zag chain structure. Study of magnetic properties revealed weak antiferromagnetic coupling within the Mn₂ dimer formed by the intermolecular hydrogen bond.     

基于双咪唑基柔性配体的一维链状铜(Ⅰ)、钴(Ⅱ)配合物的合成、结构和性质

柔性配体1,4-二亚甲基咪唑-2,3,5,6-四甲基苯(p-bitmb)与不同金属盐发生水热反应,得到两个新的配位聚合物{[Cu(Ⅰ)2Cl(p-bitmb)2][Cu(Ⅰ)Cl2]·H2O}n(1)和[CoCl2(p-bitmb)]n(2)。用单晶X-射线,元素分析,FTIR,热重分析对两个化合物进行了表征。配合物1和2都具有一维链状结构,但1中的一维链进一步通过π-π堆积和氢键作用拓展成二维超分子结构。值得注意的是配合物1合成过程中的Cu(Ⅱ)被还原为Cu(Ⅰ),推测是由于在高的合成温度下被具有还原性的咪唑环还原引起的。     

锰有机膦酸配位聚合物的合成、结构和磁性

将4-羧酸-1-萘膦酸（4-cnappH₃）与氯化锰通过水热（溶剂热）反应，得到4种不同结构的锰萘膦酸羧酸配位聚合物Mn（4-cnappH₂）₂（1），Mn（4-cnappH₂）₂（H₂O）₂（2），α-Mn（4-cnappH）（H₂O）（3）和β-Mn（4-cnappH）（H₂O）（4）。化合物1中{MnO₆}八面体与{PO₃C}四面体共角连接形成无机链，链与链之间通过膦酸配体连接形成三维框架结构，而化合物2~4都具有层状结构，层与层之间由质子化的羧酸基团通过氢键作用连接形成三维超分子结构。但这些化合物的层内拓扑结构不同，化合物2中的无机层结构包含由{MnO₆}八面体和{PO₃C}四面体共角连接的矩形12元环，化合物3中{MnO₅}三角双锥共边形成{Mn₂O₂}双核，双核之间通过{PO₃C}四面体共角连接形成包含4元环的无机层，而化合物4中则存在由{MnO₅}三角双锥共角形成的链，链间进一步通过{PO₃C}四面体共角连接形成包含3元环和4元环的无机层。磁性研究表明，所有化合物中锰离子之间都存在反铁磁相互作用。     

两个一维配位聚合物的合成、晶体结构、电化学及光学性质

合成了2个新的Robson大环配位聚合物{[Mn₂L¹（1,4-bix）₂]（ClO₄）₂·5H₂O·DMF}_n （1）和{[Cu₂L²（1,4-bix）]（ClO₄）₂}_n （2）（H₂L₁和H₂L₂分别为1,3-丙二胺与2,6-二甲酰基-4-氟苯酚和2,6-二甲酰基-4-氯苯酚通过[2+2]缩合的产物）。2个配合物通过1,4-二（1,2,4-三唑-1-甲基）苯（1,4-bix）桥连大环单元形成一维链状结构。配合物的HOMO-LUMO能带间隙通过循环伏安法、紫外-可见漫反射光谱进行了测定,结果表明有较低的能带间隙。     

两个一维配位聚合物的合成、晶体结构、电化学及光学性质

合成了2个新的Robson大环配位聚合物{[Mn₂L¹(1,4-bix)₂](ClO₄)₂·5H₂O·DMF}_n(1)和{[Cu₂L²(1,4-bix)](ClO₄)₂}_n(2)(H₂L¹和H₂L²分别为1,3-丙二胺与2,6-二甲酰基-4-氟苯酚和2,6-二甲酰基-4-氯苯酚通过[2+2]缩合的产物)。2个配合物通过1,4-二(1,2,4-三唑-1-甲基)苯(1,4-bix)桥连大环单元形成一维链状结构。配合物的HOMO-LUMO能带间隙通过循环伏安法、紫外-可见漫反射光谱进行了测定,结果表明有较低的能带间隙。     

二维含镧链异核金属化合物的合成、结构和磁性研究

水热法合成了3个层状异核金属化合物[Ln(idaH)M(ida)₂]_n·0.5nH₂O,(H₂ida=亚氨基二乙酸,Ln=Nd,M=Co (1);Ln=La,M=Co (2);Ln=La,M=Ni (3))。进行了晶体结构测定,红外光谱分析、能谱分析与磁性能分析。3个化合物除金属原子不同外具有相同的结构,其晶体都属于单斜晶系,C2/c空间群。单晶结构表明该结构含有由十配位的Ln通过羧基氧连接而成的链,六配位的3d金属(Co、Ni)交替地处在链的两边,形成了带状结构,带状链通过配体连成二维结构,通过氢键形成三维骨架。     

Two Polynuclear Fe Complexes with Boat-like Core:Syntheses,Structures and Magnetic Properties

Two novel polynuclear complexes{NaFe4（μ₄-O）(L)4（μ₂-Cl）[Fe（CN）₅NO]（H₂O）(DMF)2}（1） and{NaFe4（μ₄-O）(L)4（μ₂-OEt）[Fe（CN）₅NO]（H₂O）(DMF)₂}（2） have been prepared using the tetradentate N-（2-hydroxyethyl）-3-methoxysalicylaldimine Schiff-base ligand （H₂L） with the help of[Fe（CN）₅NO]^2-linkers,where the ligand was in situ synthesized through the condensation of o-vanillin and e...     

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。     

Molecule-Based Magnets: Ferro- and Antiferromagnetic Interactions in Copper(II)-Polyorganosiloxanolate Clusters

The magnetic behavior of the clusters [(PhSiO(2))(6)Cu(6)(O(2)SiPh)(6)].6EtOH (1), Na(4)[(PhSiO(2))(12)Cu(4)].8(n)()BuOH (2), and K(4)[(C(2)H(3)SiO(2))(12)Cu(4)].6(n)()BuOH (3) has been investigated by combined magnetic susceptibility measurements and variable-temperature EPR techniques (9.25 and 245 GHz). The six copper(II) ions in the core of 1, which approaches 6/mmm symmetry, are ferromagnetically coupled as a result of the geometry at the bridging siloxanolate oxygen atoms (Cu-O-Cu = 91.5-94.6 degrees; J = -42 cm(-)(1) with H = J S(i)().S(i)()(+1), S(7) = S(1)). The ground S = 3 spin state is split in zero field mainly due to anisotropic exchange contributions (D = 0.30 cm(-)(1)). Notably, both the magnitude and the sign of the zero-field splitting parameter have been determined from HF-EPR spectra. Large antiferromagnetic Cu-Cu interactions (J approximately 200 cm(-)(1)) and an S = 0 ground state have been detected in the tetranuclear clusters 2 and 3 as a consequence of the larger Cu-O-Cu angles. The results presented in the paper are relevant to the search for new molecule-based magnetic materials.     

Syntheses and Magnetic Properties Study of Isostructural BiM(2)BP(2)O(10) (M = Co, Ni) Containing a Quasi-1D Linear Chain Structure

We present here the structures and magnetism of two quasi-1D linear chain compounds of BiM(2)BP(2)O(10) (M = Co, Ni), which were synthesized by traditional solid-state reactions for the first time. Two title compounds crystallize in the monoclinic system with space group P2(1)/c and feature novel 3D structures with a linear chain structure of {MO(6)}(n) further connected by [BP(2)O(10)](7-) anionic groups. The results of magnetic property measurements evidence the antiferromagnetic properties of both compounds in low magnetic field and a field-dependent metamagnetic transition from the antiferromagnetic to ferromagnetic ground state of the BiCo(2)BP(2)O(10) complex.     

Synthesis,Structures and Magnetic Properties of Cyano‐bridged FeIII/MnIII Heterobimetallic 1D Chain Complexes

Using the tricyanometalate building block, (nBu₄N)[(Tp*)Fe(CN)₃] [Bu₄N⁺ = tetrabutylammonium cation; Tp*^– = hydrotris(3,5‐dimethylpyrazol‐1‐yl)borate], and bidentate Schiff base ligands, HL1 or HL2 {HL1 = 2‐[[(2‐phenylethyl)imino]methyl]phenol; HL2 = 4‐methoxy‐2‐[[(2‐phenylethyl)imino]methyl]phenol}, two heterobimetallic one‐dimensional (1D) chain complexes, [Mn(L1)₂Fe(Tp*)(CN)₃]_n ( 1 ) and [Mn(L2)₂Fe(Tp*)(CN)₃]_n ( 2 ), were synthesized. Single crystal X‐ray diffraction reveal the formation of neutral cyano‐bridged zigzag single chains in 1 and 2 . Magnetic studies demonstrate that both complexes show ferromagnetic interactions between central Fe^III and Mn^III atoms.     

Solvent‐regulated Assembly of 1D and 2D CdII Coordination Polymers with Tetrafluorophthalate: Syntheses,Structures and Properties

Two new coordination polymers [Cd(1,2‐BDC‐F₄)(H₂O)₂(py)]_n ( 1 ) and {[Cd(1,2‐BDC‐F₄)(H₂O)₂](DMF)}_n ( 2 ) were prepared from the vapor diffusion reactions of Cd^II acetate with tetrafluorophthalic acid (1,2‐H₂BDC‐F₄) under different solvent atmospheres, and structurally characterized by single‐crystal diffraction technique. Both complexes reveal polymeric coordination architectures. Complex 1 is a one‐dimensional (1D) double chain, which crystallizes in the space group, P2₁2₁2₁. In 1 , each Cd^II ion is hexacoordinate by five oxygen atoms from two terminal water and three 1,2‐BDC‐F₄ anions with a μ₃‐bridging mode, as well as one nitrogen donor from one pyridine molecule. Complex 2 is a two‐dimensional (2D) layered network, which crystallizes in the P\bar{1} space group. In 2 , each Cd^II ion is heptacoordinate by seven oxygen atoms from two terminal water and four 1,2‐BDC‐F₄ anions with a μ₄‐bridging mode. The results clearly suggest that the judicious choice of solvent systems does play a critical role in the construction of coordination frameworks with distinct dimensionality and connectivity. Their spectroscopic, thermal, and fluorescence properties have also been investigated.     

Design,Synthesis, and Properties of Molecule-Based Assemblies with Large Second-Order Optical Nonlinearities

The design, synthesis, characterization, and understanding of new molecular and macromolecular assemblies with large macroscopic optical nonlinearities represents an active field of research at the interface of modern chemistry, physics, and materials science. Challenges in this area of photonic materials typify an important theme in contemporary chemistry: to create new types of functional materials by the rational construction of supramolecular assemblies exhibiting preordained collective phenomena by virtue of “engineered” molecule–molecule interactions and spatial relationships. This review surveys several approaches to, and the microstructural and optical properties of, second-order nonlinear optical materials built from noncentrosymmetric assemblies of chromophores having large molecular hyperpolarizabilities. Such types of materials can efficiently double the frequency of incident light, exhibit other second-order nonlinear optical effects, and contribute to the knowledge base needed for new photonic device technologies. Systems described include chromophore macromolecule guesthost matrices, chromophore-functionalized glassy macromolecules, thermally crosslinked chromophore-macromolecule matrices, and intrinsically acentric self-assembled chromophoric superlattices.