Directed supramolecular assembly of infinite 1-D M(II)-containing chains (M = Cu, Co, Ni) using structurally bifunctional ligands

The directed assembly of six different M(II) complexes (M = Cu, Co, and Ni) into infinite chains has been achieved by combining anionic chelating ligands (for controlling the coordination geometry) with bifunctional ligands containing a metal-coordinating pyridyl moiety and a self-complementary hydrogen-bonding moiety. Six crystal structures are presented, and in each case, the chelating acac ligand occupies the four equatorial coordination sites leaving room for the bifunctional ligand to coordinate in the axial positions. The supramolecular chemistry, which organizes the coordination complexes into the desired infinite 1-D chains, is driven by a combination of N-H...N and N-H...O hydrogen bonds.     

Hydrothermal synthesis, structures, and photoluminescent properties of benzenepentacarboxylate bridged networks incorporating zinc(II)-hydroxide clusters or zinc(II)-carboxylate layers

The first coordination compounds of partially or wholly deprotonated benzenepentacarboxylic acid (H5L) were synthesized in the presence or absence of auxiliary 2,2'-bipyridyl (2,2'-bpy) and 1,10-phenanthroline (phen) ligands, and their crystal structures and photoluminescent properties were characterized. Their formulas are [Zn6(mu3-OH)2(L)2(H2O)6]n (1), [Zn5(mu3-OH)2(HL)2(2,2'-bpy)2]n (2), [Zn2(HL)(phen)2(H2O)2]n (3), and [Zn5(L)2(phen)4(H2O)3]n.2nH2O (4). Both 1 and 2 are three-dimensional (3D) zinc(II)-hydroxide cluster based coordination frameworks. 1 contains distorted chairlike hexanuclear Zn6(mu3-OH)2 cluster units as secondary building blocks. Each Zn6(mu3-OH)2 unit connects six others through the three-connected nodes of L5- ligands into a 3D rigid and condensed coordination network, whereas in 2, each pentanuclear Zn5(mu3-OH)2 unit connects the other six ones through the three-connected [HL]4- nodes into a 3D network in the simple cubic packing mode. 3 has two-dimensional (2D) Zn(II)-carboxylate supramolecular layers constructed from a one-dimensional (1D) coordination chain structure by hydrogen bonds of the water and mu5-[HL]4- bridges, whereas 4 has 2D coordination layers composed of Zn(II) and mu8-L5- bridges. The adjacent coordination assemblies in 3 and 4 are further extended by hydrogen bonds and pi...pi interactions into 3D supramolecular architectures. 1-4 are photoluminescent active materials, and their photofluorescent properties are closely related to their intrinsic structure arrangements.     

Synthesis and structure of ruthenium(IV) complexes featuring N-heterocyclic ligands with an N-H group as the hydrogen-bond donor: hydrogen interactions in solution and in the solid state

The synthesis and characterization of novel ruthenium(IV) complexes [Ru(η(3):η(3)-C(10)H(16))Cl(2)L] [L = 3-methylpyrazole (2b), 3,5-dimethylpyrazole (2c), 3-methyl-5-phenylpyrazole (2d), 2-(1H-pyrazol-5-yl)phenol (2e), 6-azauracile (3), and 1H-indazol-3-ol (4)] are reported. Complex 2e is converted to the chelated complex [Ru(η(3):η(3)-C(10)H(16))Cl(κ(2)-N,O-2-(1H-pyrazol-3-yl)phenoxy)] (5) by treatment with an excess of NaOH. All of the ligands feature N-H, O-H, or C═O as the potential hydrogen-bonding group. The structures of complexes 2a-2c, 2e, 3, and 5 in the solid state have been determined by X-ray diffraction. Complexes 2a-2c and 3, which contain the pyrazole N-H group, exhibit intra- and intermolecular hydrogen bonds with chloride ligands [N-H···Cl distances (?): intramolecular, 2.30-2.78; intermolecular, 2.59-2.77]. Complexes 2e and 3 bearing respectively O-H and C═O groups also feature N-H···O interactions [intramolecular (2e), 2.27 ?; intermolecular (3), 2.00 ?]. Chelated complex 5, lacking the O-H group, only shows an intramolecular N-H···Cl hydrogen bonding of 2.42 ?. The structure of complex 3, which turns out to be a dimer in the solid state through a double intermolecular N-H···O hydrogen bonding, has also been investigated in solution (CD(2)Cl(2)) by NMR diffusion studies. Diffusion-ordered spectroscopy experiments reveal an equilibrium between monomer and dimer species in solution whose extension depends on the temperature, concentration, and coordinating properties of the solvent. Preliminary catalytic studies show that complex 3 is highly active in the redox isomerization of the allylic alcohols in an aqueous medium under very mild reaction conditions (35 °C) and in the absence of a base.     

A family of new glutarate compounds: synthesis, crystal structures of: Co(H2O)5L(1), Na2[CoL2] (2), Na2[L(H2L)4/2] (3), {[Co3(H2O)6L2](HL)2}.4H2O (4), {[Co3(H2O)6L2](HL)2}.10H2O (5), {[Co3(H2O)6L2]L2/2}.4H2O (6), and Na2{[Co3(H2O)2]L8/2].6H2O (7), and magnetic properties of 1 and 2 with H2L = HOOC-(CH2)3-COOH

Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.     

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     

Engineering silver(I) coordination networks through hydrogen bonding

The silver(I) coordination networks [Ag2(mu-O2CCF3)2(mu-NN)2](infinity) exist as a polymer of macrocycles or a double-stranded polymer when NN = 1,2-C6H4[NHC(O)-4-C5H4N]2 or 1,2-C6H4[NHC(O)-3-C5H4N]2, respectively. Crystal engineering of the polymers is achieved through interchain hydrogen bonds.     

Carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine: synthesis, structure, hydrogen bond and metal directed self-assembly

Cyclooligomerization of 2,6-dichloropyrazine 4 and benzyl 2,3-dihydroxybenzoate 5 under microwave irradiation resulted in a racemic pair of ester functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 6, which was further transformed to the corresponding racemic carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 3. Both enantiomers of 3 adopt 1,3-alternate conformations with their two carboxylic acid groups pointing to opposite directions in the solid state. Enantiomers of 3 form a step-like one-dimensional supramolecular polymer via intermolecular hydrogen bond interactions between the carboxylic acids for crystals obtained in methanol. No hydrogen bonds were formed between the carboxylic acids for crystals of 3 obtained in pyridine and aqueous guanidine solutions; instead, intermolecular hydrogen bonds between the carboxylic acid groups of 3 and pyridine, as well as guanidinium ions were formed. Under metal-mediated self-assembly conditions, the pyrazinyl nitrogen atoms in 3 interacted with transition metal ions, such as Ag(I), Cu(II) and Zn(II), and resulted in the formation of four new metal-containing supramolecular complexes. Metallomacrocycles 7, 8 and 9 were formed by reactions of 3 with Ag(I) or Cu(II) ions by bridging two ligands 3 in the equatorial region via M-N coordination bonds. A one-dimensional coordination polymer 10 was generated by reaction between ligand 3 and Zn(II) ions, and a cage-based structure is presented in 10 by bridging of the cyclophane units by Zn(2+) ions via Zn-N and Zn-O bonds.     

Synthesis, structures, and magnetic properties of the copper(II), cobalt(II), and manganese(II) complexes with 9-acridinecarboxylate and 4-quinolinecarboxylate ligands

To explore the relationships between the structures of ligands and their complexes, we have synthesized and characterized a series of metal complexes with two structurally related ligands, 9-acridinecarboxylic acid (HL(1)) and 4-quinolinecarboxylate acid (HL(2)), [Cu(2)(mu(2)-OMe)(2)(L(1))(2)(H(2)O)(0.69)](n) 1, [Cu(2)(L(1))(4)(CH(3)OH)(2)] 2, [Cu(3)(L(1))(6)(CH(3)OH)(6)].3H(2)O 3, [Mn(3)(L(1))(6)(CH(3)OH)(6)].3H(2)O 4, [Co(3)(L(1))(6)(CH(3)OH)(6)].3H(2)O 5, [Cu(L(2))(2)](n) 6, [Mn(L(2))(2)(H(2)O)](n) 7, and [Co(L(2))(2)(H(2)O)](n) 8. 1 is a three-dimensional (3D) polymer with an interpenetrating NbO type network showing one-dimensional (1D) channels, whereas 2 and 3 take bi- and trinuclear structures, respectively, because of the differences in basicity of the reaction systems in preparing the three complexes. 4 and 5 have trinuclear structures similar to that of 3. In 1-5, ligand L(1) performs different coordination modes with N,O-bridging in 1 and O,O'-bridging in 2-5, and the metal ions also show different coordination geometries: square planar in 1, square pyramidal in 2, and octahedral in 3-5. 6 has a two-dimensional structure containing (4,4) grids in which L(2) adopts the N,O-bridging mode and the Cu(II) center takes square planar geometry. 7 and 8 are isostructural complexes showing 1D chain structures, with L(2) adopting the O,O-bridging mode. In addition, the intermolecular O-H...N hydrogen bonds and pi-pi stacking interactions further extend the complexes (except 1 and 6), forming 3D structures. The magnetic properties of 2-7 have been investigated and discussed in detail.     

Syntheses,crystal structures,and photophysical properties of two 2-D coordination polymers with different geometries of lead(II)

Two complexes constructed from aromatic acid and N-heterocyclic ligands have been synthesized by hydrothermal reaction: [Pb(cipt)(NDC)]_n (1) [cipt?=?2-(3-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, NDC?=?naphthalene-1,4-dicarboxylic acid] and [Pb(ipm)(BDC)₂]_n (2) [BDC?=?terephthalic acid, ipm?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol]. Single-crystal X-ray analysis shows that 1 exhibits an interesting arm-shaped chain structure. 1-D ladder chain structure is formed by N–H···O bonding interactions and further into a 2-D network by N–H···O hydrogen bonds and interchain π–π stacking interactions. Complex 2 shows a 2-D butterfly wings structure, which has been rarely reported. The structure in 2 has intermolecular N–H···O interactions, which help in construction of the 3-D framework. In 1, the coordination sphere of Pb(II) is hemi-directed, whereas the Pb(II) geometry in 2 is holo-directed. The solid-state fluorescence spectra of 1 and 2 are also investigated, as well as the ligands cipt and ipm.     

Novel silver-containing supramolecular frameworks constructed by combination of coordination bonds and supramolecular interactions

The hydrothermal reactions of AgNO(3), 4,4'-bipy, and carboxylate ligands gave rise to three supramolecular architectures, namely [Ag(bipy)].H(2)SIPA.1/2bipy.H(2)O (1), [Ag(bipy)].1/2H(2)btec.H(2)O (2), and [Ag(bipy)](2).H(2)dpstc.2H(2)O (3) (H(3)SIPA = 5-sulfoisophthalic acid, bipy = 4,4'-bipyridine, H(4)btec = 1,2,4,5-benzenetetracarboxylic acid, H(4)dpstc = 3,3',4,4'-tetracarboxydiphenyl sulfone). All complexes are extended from Ag-bipy linear chains by the combination of coordination bonds and supramolecular interactions in two different approaches. Complexes 1 and 3 comprise two-dimensional frameworks. In the two complexes, a one-dimensional ladderlike structure is first formed by the connection of a Ag-bipy chain through hydrogen bonding between a free carboxylate/bipy ligand and weak coordinative interactions between a free carboxylate ligand and silver ion. The ladderlike structure is then extended to a two-dimensional layer architecture by pi...pi interactions between bipy ligands of the Ag-bipy chains. Complex 2 possesses a three-dimensional framework. The free H(2)btec(2)(-) ligands form a two-dimensional layer network by hydrogen-bonding interactions between protonated and deprotonated carboxylate groups; meanwhile, pi.pi interactions between bipy ligands of Ag-bipy chains also result in a two-dimensional layer. The two layers are further connected by weak Ag-O interactions to generate a three-dimensional supramolecular structure.     

1，4-苯二硫乙酸配体构筑的锌(Ⅱ)及镉(Ⅱ)配合物的合成、晶体结构及荧光性质

基于1,4-苯二硫乙酸(H2L)及中性含氮配体,水热法合成了两个新的d10金属配合物[ZnClL0.5(bpp)](1)和[Cd2L(phen)4(H2O)2].L.2.78H2O(2)(bpp=1,3-di(4-pyridyl)propane,phen=1,10-phenanthroline),并通过单晶X-射线衍射、元素分析、红外光谱和热重对其结构进行了表征。结构分析表明,在配合物1中,Zn(Ⅱ)呈现四配位的扭曲四面体构型,进一步连接形成一维双链状结构。在配合物2中,Cd(Ⅱ)呈现六配位的扭曲八面体构型,并通过可能存在的氢键及π-π堆积作用,形成最终的三维超分子结构。同时,讨论了两种配合物的固体荧光性质。     

基于吡啶酰胺类配体一维带状配位聚合物的合成、结构及荧光性质

通过吡啶酰胺类配体3,5-二(4-吡啶酰胺基)吡啶(4-DPBA)与相应金属盐反应,合成了3个配位聚合物{[Zn(4-DPBA)2(NO3)2].4DMF}n(1),{[Cd(4-DPBA)2(NO3)2].4DMF}n(2)和{[Cu(4-DPBA)2(DMF)2](ClO4)2.7DMF.2H2O}n(3),并用红外光谱、元素分析、粉末及单晶X-射线衍射等方法对其进行了表征。结果表明配合物1和2是同构的,由平行的一维带状链通过氢键连接而成二维层状结构,而配合物3是由3种不同取向的一维带状链构成二维多层结构。这3个配合物最终均通过氢键连接形成三维超分子结构。研究了配合物1和2的荧光性质。     

Two New 1D Coordination Polymers Constructed from {M（H2O）（dpa）}^2＋ Subunits Bridged through [MoO4]^2- Anions （M = Copper,Cobalt and dpa = 2,2＇-Dipyridylamine）

Two new one-dimensional chain-like coordination polymers,[Cu（H2O）（dpa）- MoO4]·H2O 1 and [Co（H2O）（dpa）MoO4] 2,have been synthesized under hydrothermal reactions. Their structures were determined by single-crystal X-ray diffraction analysis. Crystal data for 1： [Cu（H2O）（dpa）MoO4]·H2O,Mr = 430.71,monoclinic,space group P21/c,a = 9.5469（10）,b = 16.6874（17）,c = 9.0799（10）A,β = 104.9100（10）°,V = 1397.8（3）A^3,Z = 4,Dc = 2.047 g/cm^3,F（000） = 852,μ = 2.449 mm-1,the final R = 0.0293 and wR = 0.0638 for 2472 independent reflections （Rint = 0.0338） and 2034 observed reflections with I 〉 2σ（I）. Crystal data for 2： [Co- （H2O）（dpa）MoO4],Mr = 408.09,monoclinic,space group P21/c,a = 10.204（2）,b = 18.933（4）,c = 6.8875（16）A,β = 102.195（3）o,Z = 4,V = 1300.5（5）A^3,Z = 4,Dc = 2.084 g/cm3,F（000） = 804,μ = 2.262 mm-1,the final R = 0.0357 and wR = 0.0693 for 3022 independent reflections （Rint = 0.0436） and 2286 observed reflections （I 〉 2σ（I））. Polymer 1 is based on a one-dimensional zigzag chain built up from {Cu（H2O）（dpa）}2＋ units bridged through the bidentate {MoO4}2- ligands. The chains extending along the c-axis are arranged alternately with two opposite orientations along the b-axis. The adjacent chains are stably packed together through π-π interactions and exhibit an interesting three-dimensional supramolecular architecture via hydrogen bonding interactions. Polymer 2 based on a one-dimensional zonal chain is built up from {Co（H2O）（dpa）}2＋ units linked by the tridentate {MoO4}2- ligands. The ribbons extend along the c-axis. In the bc layers,there are significant interactions of N-H…O-Mo hydrogen bonds and π-π overlaps of dpa ligands between adjacent ribbons.     

萘氧乙酸及咪唑构筑的锌(Ⅱ)和铜(Ⅱ)配合物的水热合成、晶体结构及荧光性质

通过水热的方法合成得到2个由萘氧乙酸及咪唑配体构筑的配合物Zn(2-naph)₂(imi)₂ (1)和2Cu(2-naph)₂(imi)₂(H₂O)·Cu(2-naph)₂(imi)₂(H₂O) (2)(2-naph=2-naphthoxyacetate,imi=imidazole),它们的结构通过X射线晶体衍射、红外光谱和元素分析得到确定。在配合物1中,锌原子与来自不同2-萘氧乙酸配体中的2个羧酸氧原子和不同的咪唑分子中的2个氮原子形成了变形的四面体的几何构型。单个分子通过N-H…O氢键连接形成了一维链,然后在C-H…π弱作用下形成了三维结构。配合物2有2个独立的铜中心,它们有几乎相同的配位环境。每个铜中心都是变形的四方锥的配位构型。来自不同的2-萘氧乙酸配体中的2个羧酸氧原子和不同的咪唑分子中的2个氮原子形成了一个相对规则的四方锥赤道平面,配位水分子位于平面上方。配合物2的分子通过N-H…O和O-H…O氢键连接形成了二维结构。2个配合物的热稳定和固体荧光性质在本文中也得到了研究和讨论。     

New oxamidato-bridged Cu(II)-Ni(II) complexes: supramolecular structures with thiocyanate ligands and hydrogen bonds. Magnetostructural studies: DFT calculations

Four new supramolecular compounds of Cu(II)-Ni(II) have been synthesized and characterized: [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(ClO(4))(2) (1), [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(PF(6))(2) (2), [Cu(oxpn)Ni(mu-NCS)(NCS) (tmen)](n) (3), and [Cu(Me(2)oxpn)Ni(mu-NCS)(NCS)(tmen)](n) (4), where oxpn = N,N'-bis(3-aminopropyl)oxamidate, Me(2)oxpn = N,N'-bis(3-amino-2,2'-dimethylpropyl)oxamidate, and tmen = N,N,N',N'-tetramethylethylenediamine. Their crystal structures were solved. Complexes 1 and 2 have the same tetranuclear cationic part but a different counteranion. The cationic part consists of two [Cu(Me(2)oxpn)Ni] moieties linked by SCN(-) bridged ligands and intra-tetranuclear hydrogen bonds. In the case of complex 3, a two-dimensional system was built, the thiocyanate ligand linking the dinuclear units gives a chain, and the chains are linked together by hydrogen bonds; intrachain hydrogen bonds are also present. For complex 4, the thiocyanate ligands produce intermolecular linkages between the dinuclear entities, giving a one-dimensional system; intrachain hydrogen bonds are also present. The magnetic properties of the four complexes were studied by susceptibility measurements vs temperature. DFT calculations were made to study the contribution of the SCN(-) and hydrogen bond bridges in the magnetic coupling.     

Syntheses,Crystal Structures and Properties of Co（Ⅱ） and Cu（Ⅱ） Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co(O2N-Hbtb)(phen)(H2O)3]·2H2O}n 1 and {[Cu3(O2N-btb)2(bipy)2(H2O)4]·4H2O}n 2(O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2'-bipyridine),were prepared through hydrothermal reactions of Co(Ⅱ) or Cu(Ⅱ) salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.     

Self-assembly using dynamic coordination chemistry and hydrogen bonding: mercury(II) macrocycles, polymers and sheets

The self-assembly of extended metal-containing arrays is described based on dynamic coordination chemistry at mercury(II) with bis(amidopyridyl) ligands to form macrocycles, polymers, or sheets which can be further organized by hydrogen bonding between amide substituents. The ligands 1,2-C6H4[NHC(O)-4-C5H4N]2, 1, 1,2-C(6)H(4)[C(O)NHCH(2)-4-C(5)H(4)N](2), 2, and 1,2-C(6)H(4)[CH(2)C(O)NHCH(2)-4-C(5)H(4)N]2, 3 can adopt polar conformations and so can confer helicity in their complexes. Several macrocycles of formula [(HgX(2))(2)(micro-LL)(2)] (LL = 1, 2), with tetrahedral mercury(II) centers, were prepared in which individual molecules are further self-assembled via hydrogen bonding in the solid state to form one- or two-dimensional polymers or sheets. In one case, a one-dimensional polymer [((HgX2)-(mu-3))n] was formed. It is shown that the mercury(II) centers can be six-coordinate in forming the sheet structure [((HgX2)(mu-2)2)n], in which there are particularly large pores.     

Diastereospecific and diastereoselective syntheses of Ruthenium(II) complexes using N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N and their oxidation to imine ligands

Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a; 4-CH3O-C6H4, 1b; 2,6-(CH3)2-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)2]2+, [Ru(eta5-C5H5)L]+ (L = CH3CN, CO), or [Ru(eta6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)2(1b)](PF6)2, 2b; [Ru(2,2'-bipyridine)(2)(1c)](PF6)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta6-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.     

Near-infrared luminescent and magnetic cyano-bridged coordination polymers Nd(phen)n(DMF)m[M(CN)8] (M = Mo, W)

New cyano-bridged coordination polymers [Nd(phen)(2)(DMF)(2)(H(2)O)Mo(CN)(8)]·2H(2)O (1) and [Nd(phen)(DMF)(5)M(CN)(8)]·xH(2)O [M = Mo (2), W (3); phen = 1,10-phenanthroline] have one-dimensional structures with variable number of phenanthroline ligands. Compounds exhibit photoluminescence in the near-infrared region and ferromagnetic Nd(3+)-M(5+) interactions.     

Copper(I) coordination chemistry of (pyridylmethyl)amide ligands

Copper(I) chloro complexes were synthesized with a family of ligands, HL(R) [HL(R) = N-(2-pyridylmethyl)acetamide, R = null; 2-phenyl-N-(2-pyridylmethyl)acetamide, R = Ph; 2,2-dimethyl-N-(2-pyridylmethyl)propionamide, R = Me3; 2,2,2-triphenyl-N-(2-pyridylmethyl)acetamide, R = Ph3)]. Five complexes were synthesized from the respective ligand and cuprous chloride: [Cu(HL)Cl]n (1), [Cu2(HL)4Cl2] (2), [Cu2(HL(Ph))2(CH3CN)2Cl2] (3), [Cu2(HL(Ph)3)2Cl2] (4), and [Cu(HL(Me)3)2Cl] (5). X-ray crystal structures reveal that for all complexes the ligands coordinate to the Cu in a monodentate fashion, and inter- or intramolecular hydrogen-bonding interactions formed between the amide NH group and either amide C=O or chloro groups stabilize these complexes in the solid state and strongly influence the structures formed. Complexes 1-5 display a range of structural motifs, depending on the size of the ligand substituent groups, hydrogen bonding, and the stoichiometry of the starting materials, including a one-dimensional coordination polymer chain (1) and binuclear (2-4) or mononuclear (5) structures.