Syntheses,structures and magnetic properties of three cobalt(II) coordination polymers based on flexible itaconic acid ligands

Transition Metal Chemistry - Three Co(II) coordination polymers, namely [Co(ia)(bpe)0.5(H2O)]n (1), {[Co(ia)(bib)(H2O)]·H2O}n (2) and {[Co(ia)(btmb)(H2O)]·H2O}n (3)...     

Crystal structures and magnetic properties of manganese(II) and nickel(II) complexes constructed from 1,3,5-tris(carboxymethoxy)benzene acid ligand

Transition Metal Chemistry - Two coordination polymers, namely {[Mn2(HL)2(bpe)(H2O)8]·5H2O}n (1) and {[Ni3(L)2(bpe)3(H2O)6]·3H2O}n (2)...     

The Length of Substituents on Ligands Regulates the Structural Diversity of Coordination Polymers

Russian Journal of Coordination Chemistry - Three coordination polymers, namely, {[Co(L1)(HBTC)]·0.5L1}n (I), {[Co(L2)(HBTC)]·H2O}n (II), {[Co(L3)(HBTC)]·H2O}n (III), have been...     

Two Zinc(II)/Cadmium(II) Coordination Polymers Constructed by Semirigid Carboxylic Acid Ligand: Syntheses,Structures, and Photoluminescence Properties

Russian Journal of Coordination Chemistry - Two new coordination polymers {[Zn(HL)(HBpp)] · H2O}n (I) and [Cd(HL)(HBpe)]n (II) (H4L = 5-(2,3-dicarboxy phenoxy) isophthalic acid, Bpp =...     

Systematic exploration of a rutile-type zinc(II)-phosphonocarboxylate open framework: the factors that influence the structure

To systematically explore the assembly mechanism of a rutile-type open framework of {[Zn(3)(pbdc)(2)]·2H(3)O}(n) (3) (H(4)pbdc = 5-phosphonobenzene-1,3-dicarboxylic acid) constructed by 3-connected pbdc ligands and 6-connected Zn(3)(CO(2))(4)(PO(3))(2) secondary building units (Zn(3)-SBUs), three major factors including solvothermal procedures, types of solvents and amines, are taken into consideration. Seven novel structures, namely {[Zn(5)(pbdc)(2)(OH)(2)(H(2)O)(4)]·4H(2)O}(n) (1), {[Zn(3)(pbdc)(2)·H(2)O]·(Htea)·H(3)O·2-5(H(2)O)}(n) (2), {[Zn(3)(pbdc)(2)](H(3)O)(2)(dma)}(n) (4), {[Zn(2)(pbdc)(taea)]·3H(2)O}(n) (5), {[Zn(3)(pbdc)(2)(Hpda)(2)]·2H(2)O}(n) (6), {[Zn(5)(pbdc)(2)(Hpbdc)(2)]·2H(2)pz·9H(2)O}(n) (7), {[Zn(3)(pbdc)(2)]·Hpd·H(3)O·4H(2)O}(n) (8) are obtained. The results indicate that the layered-solvothermal method and the isopropanol solvent play crucial roles in the construction of the special anionic open framework of [Zn(3)(pbdc)(2)](2-). Changing these two factors led molecular assembly away from the rutile-type open framework. However, amines play a variable role in the framework, which means that by using appropriate amines, molecular assembly could generate the open framework of [Zn(3)(pbdc)(2)](2-) with pores decorated by amines. These results suggest a different approach towards decorating pores in anionic frameworks with precise structural information.     

EFFECT OF SUBSTITUENT IN MALONATE ANIONS ON THE STRUCTURE OF Zn(II) COORDINATION POLYMERS

Journal of Structural Chemistry - New zinc (II) coordination compounds with benzylmalonic [Zn(Bzmal)(EtOH)(H2O)]n (1) and cyclobutane-1,1-dicarboxylic {[Zn4(Cbdc)4(H2O)4]·2.5H2O}n (2) acid...     

Syntheses,Structures, and Properties of Two Cd(II)/Zn(II) Complexes with 1,2,4-triazole Derivatives

Russian Journal of Coordination Chemistry - Two new coordination polymers, {[Cd(Hmph)(Itmb)] ? H2O}n (I) and [Zn(Hmph)(Bpt)2]n (II) (H2Hmph = homophthalic acid, Itmb =...     

Flexible and shape-selective guest binding at Cu(II) axial sites in 1-dimensional Cu(II)-1,2-bis(4-pyridyl)ethane coordination polymers

A series of guest-binding Cu(II) coordination polymers, {[Cu(bpetha)2(acetone)2].2PF6}n (bpetha = 1,2-bis(4-pyridyl)ethane) (1), {[Cu(bpetha)2(DMF)2].2PF6}n (2), {[Cu(bpetha)(2)(MeCN)(2)].2PF6.2MeCN}n (3), {[Cu(bpetha)2(H2O)2].2PF6.3THF.2H2O}n (4), {[Cu(bpetha)2(H2O)2].2PF6.3dioxane}n (5), and {[Cu(bpetha)2(H2O)2].2PF6.2-PrOH.2H2O}n (6), have been synthesized and crystallographically characterized. Their framework stabilities and guest-exchange properties have also been investigated. All compounds form a similar framework motif, a "double chain", in which the bpetha ligands bridge Cu(II) centers to form 1-D [Cu(bpetha)2]n double chains. A variety of Lewis base guest molecules, such as H2O, acetone, DMF, MeCN, THF, dioxane, and 2-PrOH, are incorporated into the assembly of the 1-D double chains. These chains flexibly change their forms of assembly in a guest-dependent manner. Interestingly, acetone, DMF, and MeCN guests with a carbonyl or cyanide group coordinate directly to the axial sites of the Cu(II) centers; in contrast, THF, dioxane, and 2-PrOH guests with an ether or alcohol group are incorporated into the frameworks not via coordination bonds but via weak interactions (hydrogen bonds and van der Waals forces). This selectivity is probably due to steric effects at coordinated oxygen or nitrogen atoms of the guests. Crystal-to-crystal transformations triggered by guests are observed, during which guests coordinated to the Cu(II) axial sites are readily removed and replaced by other guests.     

Temperature-directed structural recurrence in low-symmetric Co(II) complexes and nanocrystals

Low-symmetric complexes {[Co(μ(2)-L)(H(2)O)(2)]·H(2)O}(n) (1) and {[Co(μ(3)-L)(H(2)O)]·0.5H(2)O}(n) (2) and corresponding nanocrystals were obtained, which exhibit structural recurrence behaviour at various temperatures as well as changes of chiral, nonlinear optical and ferroelectric properties.     

Synthesis,Crystal Structures,and Magnetic Properties of Two Manganese(II)/Cobalt(II) Coordination Polymers Constructed by Nitrogenous Carboxylic Acid

Russian Journal of General Chemistry - Two new coordination polymers, {[Mn2(L)(H2O)2]·H2O}n (1) and {[Co2(L)(H2O)2]·H2O}n (2) (H4L = 2-(2,4,6-tricarboxylphenyl)-6-carbxoylbenzimi-dazole),...     

Hydrothermal synthesis, structure, and luminescent properties of selected Zn(II)/Cd(II) coordination polymers constructed from 3,5-bis(x-pyridyl)-1,2,4-triazole (x = 3, 4)

Utilizing 3,5-bis(x-pyridyl)-1,2,4-triazole (x-Hpytz, x = 3; x = 4) as multidentate ligands, six novel coordination polymers with Zn(II) or Cd(II) metal ions were prepared: [Zn(3-pytz)(0.5)(OH)(0.5)Cl](n) (1, 1D ladder), {[Zn(3-Hpytz)(H(2)O)(4)] [Zn(3-Hpytz)(H(2)O)(3)·SO(4)]SO(4)·5H(2)O}(n) (2·5H(2)O, 1D chain), [Cd(3-Hpytz)(SO(4))](n) (3, 3D framework), {[Cd(3-Hyptz)SO(4)·3H(2)O]·2H(2)O}(n) (4·2H(2)O, 1D chain), [Zn(4-pytz)Cl](n) (5, 3D framework) and [Zn(2)(4-pytz)(SO(4))(OH)](n) (6, 3D framework). All compounds were obtained from hydrothermal reactions, with the exception of compound 4 which was obtained by solvent diffusion at room temperature. All compounds were characterized by FTIR, elemental analysis and TGA analysis and their structures were determined by X-ray diffraction. All compounds exhibited substantial thermal stability and showed photofluorescent properties that resulted from ligand π-π* transition.     

Co(II), Mn(II) and Cu(II)-directed coordination polymers with mixed tetrazolate-dicarboxylate heterobridges exhibiting spin-canted, spin-frustrated antiferromagnetism and a slight spin-flop transition

Three new paramagnetic ion-directed coordination frameworks, {[Co(4)(H(2)O)(2)(μ(3)-OH)(2)(atz)(2)(nip)(2)]·3H(2)O}(n) (1), {[Mn(4)(H(2)O)(2)(μ(3)-OH)(2)(atz)(2)(nip)(2)]·H(2)O·MeOH}(n) (2) and {[Cu(2)(H(2)O)(μ(3)-OH)(atz)(nip)]·2H(2)O}(n) (3), were, respectively, obtained by solvo-/hydrothermal reactions of 5-amino-1H-tetrazole (Hatz), 5-nitroisophathalic acid (H(2)nip) with an inorganic Co(II), Mn(II) or Cu(II) salt. The former two complexes are two-dimensional (2D) covalent layers built from butterfly-shaped tetranuclear M(4)(μ(3)-OH)(2) clusters and double atz(-) and nip(2-) linkers. Whereas complex 3 is a 3D framework with scarcely observed corner-sharing Cu(3)(μ(3)-OH) Δ-chains extended by nip(2-) linkages, in which the anionic atz(-) ligand acts as a reinforcement to consolidate the Δ-chain. Magnetically, due to the interplay of the anisotropy of spin carrier and magnetic exchange interactions from the adjacent spin carriers, the complexes exhibit spin-canted antiferromagnetism with a Néel temperature lower than 2.0 K for 1 and an antiferromagnetic ordering with a slight field-induced spin-flop transition for 2. In contrast, complex 3 with a local Kagomé sublattice displays spin-frustrated antiferromagnetic behavior with magnetic ordering at 16.0 K.     

Synthesis,Crystal Structure,and Photoluminescent Properties of Two Porous Pillared-layer Metal-organic Frameworks Constructed by Benzene-1,3,5-tricarboxylic Acid and Bisimidazole Ligands

Russian Journal of Coordination Chemistry - Two pillared layer metal organic frameworks, namely {[Co3(Btc)2(Bib)3(H2O)2] · 7H2O}n(I) and {[Cd2(Btc)(Bib)2(Fma)(H2O)] · H2O}n (II), where...     

Construction of a Set of Cadmium（Ⅱ） Coordination Polymers with Atza and 2,2′-Bipy or 1,10-Phen Ligands （Atza=5-Aminotetrazole-1-acetato Anion）

Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd(Ⅱ) coordination polymers, {[Cd(atza)(H2O)(2,2′-bipy)]ClO4}n (1), {[Cd(atza)(H2O)(1,10-phen)]ClO4 }n (2), {[Cd(atza)(H2O)(2,2′-bipy)]NO3}n (3) and {[Cd(atza)2 (1,10-phen)]·0.5H2O}n (4). Single-crystal X-ray diffraction analysis reveals that each Cd(Ⅱ) ion has a distorted octahedral coordination geometry in 1-4, and the Cd(Ⅱ) ion centers are connected through the tridentate atza bridging ligands to form a 2D layer (1-3) or ID chain (4) structure. The fluorescent properties of 2 and 4 are also discussed.     

Blue Luminescent Zinc(II)-and Cadmium(II)-1,4-phenylenediacetate Complexes

1 INTRODUCTION The crystal engineering and design of solid-state coordination polymers have become a very attrac- tive field in recent years[1～4]. Many interesting fra- meworks with intriguing potential applications have been obtained through the self-assembly of selected metal centers and carboxylate ligands[5, 6]. Compared with aromatic carboxylate ligands such as terephtha- lic acid[7, 8], benzene tricarboxylic acid[9, 10], benzene tetracarboxylic acid[11, 12] and so on, those ligands …     

Extended three-dimensional supramolecular architectures derived from trinuclear (bis-beta-diketonato)copper(II) metallocycles

Neutral trinuclear (triangular) copper(II) complexes of type [Cu3L3] incorporating the 1,4-aryl linked bis-beta-diketonato bridging ligands, 1,1-(1,4-phenylene)-bis(butane-1,3-dione) (H2L2), 1,1-(1,4-phenylene)-bis(pentane-1,3-dione) (H2L3) and 1,1-(1,4-phenylene)-bis(4,4-dimethylpentane-1,3-dione) (H2L4) have been demonstrated to react with selected heterocyclic nitrogen donor bases to generate extended supramolecular architectures whose structures have been confirmed by X-ray diffraction. Thus on reaction with 4,4'-bipyridine (bipy), [Cu3(L2)3] yields polymeric structures of type {[Cu3(L2)3(bipy)(THF)] x 2.75THF}n and {[Cu3(L2)3(bipy)(THF)] x bipy x 0.75THF}(n) while with pyrazine (pyz), {[Cu3(L2)3(pyz)] x 0.5THF}n was obtained. Each of these extended structures contain alternating triangle/linker units in a one-dimensional polymeric chain arrangement in which two of the three copper sites in each triangular 'platform' are formally five-coordinate through binding to a heterocyclic nitrogen atom. Interaction of the multifunctional linker unit hexamethylenetetramine (hmt) with [Cu3(L3)3] afforded an unusual, chiral, three-dimensional molecular framework of stoichiometry [Cu3(L3)3(hmt)]n. The latter incorporates the trinuclear units coordinated to three triply bridging hmt units. In marked contrast to the formation of the above structures incorporating bifunctional linker units and five-coordinate metal centres, the trinuclear platform [Cu3(L2)3] reacts with the stronger difunctional base 1,4-diazabicyclo[2.2.2]-octane (dabco) to yield a highly symmetric trigonal columnar species of type {[Cu3(L4)3(dabco)3] x 3H2O}n in which each copper centre is octahedrally coordinated.     

Lanthanide-3d cyanometalate chains Ln(III)-M(III) (Ln=Pr, Nd, Sm, Eu, Gd, Tb; M=Fe) with the tridentate ligand 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tptz): evidence of ferromagnetic interactions for the Sm(III)-M(III) compounds (M=Fe, Cr)

A series of cyanide-bridged chain mixed Fe(III)/Ln(III) (Ln=Pr, Nd, Sm, Eu, Gd, Tb) complexes with the tridentate ligand 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tptz) used as a capping group has been prepared. Reactions of tptz and LnCl3 with K3Fe(CN)6 yield a family of air-stable 1-D compounds {[Pr(tptz)(H2O)4Fe(CN)6].8H2O}infinity, {[Nd(tptz)(H2O)4Fe(CN)6].8H2O}infinity, {[Sm(tptz)(H2O)4Fe(CN)6].8H2O}, {[Eu(tptz)(H2O)4Fe(CN)6].6H2O}infinity, {[Gd(tptz)(H2O)4Fe(CN)6].6H2O}infinity, and {[Tb(tptz)(H2O)4Fe(CN)6].8H2O}infinity. Temperature dependent magnetic susceptibility studies of reveal that in , the Sm(III) and Fe(III) ions are ferromagnetically coupled with 3-D ordering occurring below 3.5 K. The appearance of the frequency dependent out-of-phase signal is explained in terms of an ordering with a spin glass-like behavior. To compare the magnetic behavior of with related compounds, {[Sm(tptz)(H2O)4Co(CN)6].8H2O}infinity and {[La(tptz)(DMF)(H2O)3Fe(CN)6].5H2O}infinity, {[Sm(tmphen)(DMF)3(H2O)Fe(CN)6].2H2O}infinity, {[Sm(tmphen)2(H2O)2Fe(CN)6].MeOH.13H2O}infinity and {[Sm(tmphen)2(H2O)2Cr(CN)6].MeOH.9H2O}infinity with 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) were also prepared.     

Cobalt(II)-(dpyo)-dicarboxylate networks: unique H-bonded assembly and rare bridging mode of dpyo in one of them [dpyo = 4,4'-dipyridyl N,N'-dioxide

Polymeric networks, {[Co(dpyo)(ox)]}(n) (1), {[Co(dpyo)(fum)(H(2)O)(2)]}(n) (1) and {[Co(dpyo)(tp)(H(2)O)(2)] x [Co(H(2)O)(6)] x (tp) x (H(2)O)}(n) (3) [ox = oxalate dianion, fum = fumarate dianion, tp = terephthalate dianion and dpyo = 4,4'-dipyridyl N,N'-dioxide] have been synthesized and characterized by single crystal X-ray diffraction analyses. The structural determination reveals 1 and 2 are covalent bonded 2D networks of 4,4 topology and of these, complex 2 undergoes a H-bonding scheme resulting in a 3D supramolecular architecture. Complex 3 is a 1D coordination polymer built up by almost collinear hexacoordinated Co(ii), doubly bridged by a tp carboxylate group and a dpyo oxygen, which in combination with lattice [Co(H(2)O)(6)](2+), tp and water molecules shows an unprecedented 3D supramolecular network through H-bonding. In the polymer the dpyo shows novel mu-4,4 bridging mode towards the cobalt ion. Low temperature magnetic interaction reveals antiferromagnetic coupling in all of the complexes.     

Two Heteroligand Cd(II)-coordination Polymers: Crystal Structures and Anti-Lung Cancer Activity Evaluation

Russian Journal of Coordination Chemistry - Two new Cd(II) containing coordination polymers, namely {[Cd(Dib)(1,4-Ndc)] · H2O}n (I, Dib = 1,4-di(1H-imidazol-1-yl)butane, 1,4-H2Ndc =...     

Magnetic spongelike behavior of 3D ferrimagnetic {[Mn(II)(imH)]2[Nb(IV)(CN)8]}n with Tc = 62 K

Fully reversible room temperature dehydration of 3D {Mn(II)2(imH)2(H2O)4[Nb(IV)(CN)8] x 4 H2O}n (1; imH = imidazole) of Tc = 25 K results in the formation of 3D ferrimagnet {[Mn(II)(imH)]2[Nb(IV)(CN)8]}n (2), with Tc = 62 K, the highest ever known for octacyanometalate-based compounds. The dramatic magnetostructural modifications in 2 provide the first example of magnetic spongelike behavior in an octacyanometallate-based assembly.