Three 4-connected nickel coordination polymers affording a 3-D CdSO4 network and two 2-D (4,4) networks

The self-assembly reaction of 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and Ni(II) salts gives three coordination polymers {[Ni(btb)₂(NCS)₂]?·?H₂O} _n (1), [Ni(btb)₂(NCO)₂] _n (2), and [Ni(btb)₂Cl₂] _n (3). Compound 1 is comprised of a twofold interpenetrating 4-connected 6⁵?·?8-CdSO₄ 3-D coordination network. Compounds 2 and 3 are neutral 2-D (4,4) networks with the ABAB?···?and ABCABC?···?stacking modes, respectively. The thermal stabilities of 1–3 were investigated.     

Three cobalt coordination polymers based on bis(1,2,4-triazol-1-ylmethyl)benzene positional isomer ligands and thiocyanate

The reaction of three positional isomer ligands of bis(1,2,4-triazol-1-ylmethyl)benzene and Co(NCS)₂ gives three coordination polymers [Co(obtz)₂(NCS)₂] _n (1), [Co(mbtz)₂(NCS)₂] _n (2), and {[Co(bbtz)₂(NCS)₂]?·?2DMF} _n (3). Polymers 1 and 2 are comprised of similar 1-D double chains. In 1, each chain forms π–π stacking interactions with four adjacent chains (two above and two below) to extend to a 3-D supramolecular network. Polymer 3 is a neutral 2-D (4,4) network. The dangling NCS^? inserts into the window of adjacent layers in a mutual relationship and result in a 2-D?→?3-D polythreaded network in 3. The thermal stability and the diffuse reflectance UV-Vis spectroscopy of 1, 2, and 3 were measured.     

Construction of zinc–organic frameworks by flexible aliphatic dicarboxylates plus 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole ligand

Three new Zn(II) complexes, [Zn(ox)(imb)] (1), [Zn₂(mal)₂(imb)₂] (2), and [Zn(suc)(imb)]·H₂O (3) (imb = 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole, H₂ox = oxalic acid, H₂mal = malonic acid, H₂suc = succinic acid), have been synthesized and structurally characterized. Complex 1 is a 3-D framework with a 4-connected diamond topology with the topological notation of 6⁶. Complex 2 exhibits 2-D layers with (6,3) networks. Complex 3 displays a 3-D framework constructed through unusual 2-D → 3-D parallel interpenetration of corrugated 2-D (6,3) networks. IR spectra, PXRD patterns, thermogravimetric curves, and photoluminescence spectra are addressed.     

Ten complexes constructed by two reduced Schiff base tetraazamacrocycle ligands: syntheses,structures, magnetic and luminescent properties

Ten new complexes, [Cu₂(L¹)(NO₃)₂]·2H₂O (1), [Cu₄(L¹)₂]·4ClO₄·H₂O (2), [Cu₂(L¹)(H₂O)₂]·(adipate) (3), [Cu₆(L¹)₂(m-bdc)₄]·2DMF·5H₂O (4), [Cu₂(L¹)(Hbtc)]·5H₂O (5), [Cu₂(L¹)(H₂O)₂]·(ntc)·3H₂O (6), [Co₂(L²)]·[Co(MeOH)₄(H₂O)₂] (7), [Co₃(L²)(EtOH)(H₂O)] (8), [Ni₆(L²)₂(H₂O)₄]·H₂O (9) and [Zn₄(L²)(OAc)₂]·0.5H₂O (10), have been synthesized. 1 displays a [Cu₂(L¹)(NO₃)₂] monomolecular structure. 2 shows a supramolecular chain including [Cu₂L¹]²⁺. In 3, two Cu(II) ions are connected by L¹ to form a [Cu₂(L¹)(H₂O)₂]²⁺ cation. In 4, the m-bdc anions bridge Cu(II) ions and L¹ anions to form a layer. Both 5 and 6 display 3-D supramolecular structures. 7 consists of both [Co₂L²]^2? and [Co(MeOH)₄(H₂O)₂]²⁺ units. 8 and 9 show infinite chain structures. In 10, Zn(II) dimers are linked by L² to generate a 3-D framework. The magnetic properties for 4 and 8 and the luminescent property for 10 have been studied.     

Nuclease activity of redox/non-redox active binuclear transition metal mixed-polypyridine complexes: [M2(1,4-tpbd)(diimine)2(H2O)2]4+, M = Zn,Co, Ni,Cd, diimine = phen,bpy, dafo

Seven new transition metal complexes formulated as [M₂(1,4-tpbd)(diimine)₂(H₂O)₂]⁴⁺ [M = Zn, Co, Ni, Cd; 1,4-tpbd = N,N,N′,N′-tetrakis(2-pyridylmethyl)benzene-1,4-diamine; diimine is a N,N-donor heterocyclic base like 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 4,5-diazafluoren-9-one (dafo)] have been synthesized and structurally characterized by X-ray crystallography: [Zn₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (1), [Zn₂(1,4-tpbd)(bpy)₂(H₂O)₂]⁴⁺ (2), [Co₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (3), [Ni₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (4), [Ni₂(1,4-tpbd)(bpy)₂(H₂O)₂]⁴⁺ (5), [Ni₂(1,4-tpbd)(dafo)₂(H₂O)₂]⁴⁺ (6) and [Cd₂(1,4-tpbd)(phen)₂(H₂O)₂]⁴⁺ (7). Single crystal diffraction reveals that the metals in the complexes are all in a distorted octahedral geometry. The interactions of the seven complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescence, circular dichroism spectroscopy and viscosity measurements. The apparent binding constants (K_app) are calculated to be 5.2?×?10⁵ M^?1 for 1, 1.05?×?10⁵ M^?1 for 2, 5.76?×?10⁵ M^?1 for 3, 4.57?×?10⁵ M^?1 for 4, 1.29?×?10⁵ M^?1 for 5, 1.7?×?10⁵ M^?1 for 6, 2.53?×?10⁵ M^?1 for 7, the binding propensity to the calf thymus DNA in the order: 3 (Co-phen) > 1 (Zn-phen) > 4 (Ni-phen) > 7 (Cd-phen) > 6 (Ni-dafo) > 5 (Ni-bpy) > 2 (Zn-bpy). Furthermore, these complexes display efficient oxidative cleavage of supercoiled DNA; the Zn(II)/H₂O₂ and Cd(II)/H₂O₂ systems efficiently cleave DNA attributed to the peroxide ion coordinated to the Zn(II) and Cd(II), which enhanced their nucleophilicity, this is rare.     

Syntheses and crystal structures of four new fpa-metal complexes through in situ ligand reaction

Four new fpa-metal complexes, [Co(fpa)₂(H₂O)₂] (1), [Cu(fpa)₂(H₂O)] (2), [Zn₂(fpa)₄(bpp)₂] _n (3), and {[Zn(bpy)(H₂O)₄]?·?2(fpa)} _n (4), have been synthesized and fully characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, and thermogravimetric analysis (TGA), (Hfpa?=?2,2-difluoro-2-(pyridine-2-yl)acetate, bpp?=?1,3-bis(4-pyridyl)propane, bpy?=?4,4′-bipyridine). X-ray diffraction analyses reveal that 1 and 2 with 0-D structures are both extended into 3-D supramolecular networks through hydrogen bonds and π···π interactions. Complex 3 with chiral centers possesses a 1-D structure constructed by two kinds of bpp molecules and four kinds of fpa^? molecules with different conformations, with bbp and fpa^? bridging and capped ligands, respectively. In 4, bpy links [Zn(H₂O)₄]²⁺ into a 1-D polymeric cationic chain and uncoordinated fpa^? compensates the framework charge. The results of TGA reveal that fpa^? decomposes through two processes. Both 3 and 4 show strong fluorescence in the solid state at room temperature.     

New polynuclear compounds based on N-benzyliminodipropionic acid: solution studies,synthesis, and X-ray crystal structures

Three new polynuclear compounds based on a dicarboxylic acid ligand are reported. In particular, two Cu(II) coordination compounds, [Cu₂(H₂O)₆(Hbzlidp)₂](CF₃SO₃)₂·2H₂O (1) and [Cu(NO₃)(Hbzlidp)]_∞ (2) (bzlidp^2? = N-benzyliminodipropionate anion), and a Ni(II) dinuclear compound, [Ni₂(H₂O)₄(bzlidp)₂] (3), were synthesized and characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. Different structures were obtained depending on the reaction conditions. The structural analyses reveal that 1 was formed by dinuclear [Cu₂(H₂O)₆(Hbzlidp)₂]²⁺ units built by two copper(II) ions joined through two Hbzlidp^? ligands, while 2 was formed by pairs of Cu(II) centers bridged by four syn,syn carboxylate groups to generate “paddle wheel” units. The dinuclear copper units are arranged in a rhombus type grid, in a 2-D layer structure. In both cases, the N was protonated and not coordinated to the metal center. Compound 3 was formed by [Ni₂(H₂O)₄(bzlidp)₂] neutral dinuclear units, with octahedral Ni(II) centers. Solution studies of the ligand–M(II) systems (M(II) = Mn, Co, Ni, Cu, Zn, Cd, and Pb) were also carried out.     

Self-assembly of 1-D, 2-D,and 3-D transition-metal coordination polymers based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide

Three coordination polymers, {[Co(C₁₀H₅N₃O₅)(H₂O)₂]·H₂O}_n (1), {[Mn₃(C₁₀H₅N₃O₅)₂Cl₂(H₂O)₆]·2H₂O}_n (2), and {[Cu₃(C₁₀H₄N₃O₅)₂(H₂O)₃]·4H₂O}_n (3), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H₃DCImPyO), were synthesized under hydrothermal conditions. The polymers showed diverse coordination modes, being characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray structure analysis. In 1, the HDCImPyO^2? generated a 1-D chain by adopting a μ₂-kN, O : kN′, O′ coordination mode to bridge two Co(II) ions in two bis-N,O-chelating modes. In 2, the HDCImPyO^2? adopted a μ₃-kN, O : kO′, O′′ : O′′′ coordination mode to bridge two crystallographically independent Mn(II) ions, forming a 2-D hcb network with {6³} topology. In 3, by adopting μ₄-kN, O : kO′, O′′ : kN′′, O′′′ : O′′′′ coordination, DCImPyO^3? bridged three crystallographically independent Cu(II) ions to form a 3-D framework having the stb topology.     

Synthesis,crystal structures,and fluorescence properties of (RS)-2-methylglutarato Zn(II), Cd(II) complexes

Reactions of fresh M(OH)₂ (M = Zn²⁺, Cd²⁺) precipitate and (RS)-2-methylglutaric acid (H₂MGL), 2,2′-bipyridine (bipy), or 1,10-phenanthroline (phen) in aqueous solution at 50°C afforded four new metal–organic complexes [Zn₂(bipy)₂(H₂O)₂(MGL)₂] (1), [Zn₂(phen)₂(H₂O)(MGL)₂] (2), [Cd(bipy)(H₂O)(MGL)] · 3H₂O (3), and [Cd(phen)(H₂O)(MGL)] · 2H₂O (4), which were characterized by single crystal X-ray diffraction, IR spectra, TG/DTA analysis as well as fluorescence spectra. In 1, the [Zn(bipy)(H₂O)]²⁺ moieties are linked by R- and S-2-methylglutarate anions to build up the centrosymmetric dinuclear [Zn₂(bipy)₂(H₂O)₂(MGL)₂] molecules. In 2, the 1-D ribbon-like chains [Zn₂(phen)₂(H₂O)(MGL)₂] _n can be visualized as from centrosymmetric dinuclear [Zn₂(phen)₂(H₂O)₂(MGL)₂] units sharing common aqua ligands. Both 3 and 4 exhibit 1-D chains resulting from [Cd(bipy)(H₂O)]²⁺ and [Cd(phen)(H₂O)]²⁺, respectively, bridged alternately by R- and S-2-methylglutarate anions in bis-chelating fashion. The intermolecular and interchain π···π stacking interactions form supramolecular assemblies in 1 and 1-D chains in 2–4 into 2-D layers. The hydrogen bonded lattice H₂O molecules are sandwiched between 2-D layers in 3 and 4. Fluorescence spectra of 1–4 exhibit LLCT π → π* transitions.     

Syntheses,structures, and luminescence of two Zn(II) coordination polymers based on 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole and carboxylates

Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H₃PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn₂(IPT)(DSDB)(OH)]_n (H₂DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn₂(IPT)(PrIDC)(H₂O)]_n (H₃PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]_n chains and DSDB^2? connectors, in which the DSDB^2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·12²), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT^? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.     

Syntheses,crystal structures and characterization of divalent transition metal sulfonate complexes with O-phenanthroline

Two new complexes, [Zn(phen)₂(H₂O)₂]2L·H₂O (1) and [Cu(phen)(L)(H₂O)₂]L·3H₂O (2), where HL?= 4-aminobenzenesulfonic acid and phen = o-phenanthroline, have been synthesized and their crystal structures determined by X-ray diffraction. In the complexes the Cu(II) and Zn(II) atoms revealed two different coordination environments. Complex 1 consists of a cation [Zn(phen)₂(H₂O)₂]²⁺, in which Zn(II) is six-coordinated by four nitrogen atoms from two o-phenanthroline molecules and by two water molecules. Complex 2 has two crystallographically unique Cu(II) ions, where Cu(II) ion is five-coordinate with two nitrogen atoms of o-phenanthroline, two water molecules and one sulfonate oxygen atom. The electrochemical behavior and FT-IR of the two compounds have also been studied in detail.     

Syntheses,structures, and properties of four coordination compounds constructed from asymmetric semi-rigid V-shaped multicarboxylate ligand

Four new compounds, [Mn(HL)(phen)₂(H₂O)] (1), [Ni(HL)(phen)₂(H₂O)] (2), [Zn(HL)(4,4′-bipy)_1.5(H₂O)] _n ?·?2nH₂O (3) and [Zn₂(HL)₂(H₂O)₆] (4), have been synthesized from an asymmetric semi-rigid V-shaped multicarboxylate 4-(4-carboxy-phenoxy)-phthalic acid (H₃L) with 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy) as auxiliary ligands. Single-crystal X-ray diffraction analysis reveals that 1, 2 and 4 have 0-D structures with 3-D supramolecular frameworks formed by intermolecular hydrogen bonds. Compound 3 shows a 1-D infinite ribbon bridged by 4,4′-bipy, which further forms a 3-D supramolecular architecture by π–π stacking interactions and hydrogen bonds. Thermal stabilities of 1–4 and luminescence properties of 3 and 4 have also been investigated.     

Syntheses,crystal structures,and characterization of three metal–organic complexes with 2,2′-biphenyldicarboxylic acid and phenanthroline ligands

Three complexes constructed with 2,2′-biphenyldicarboxylic acid, multidentate nitrogen donors, and metal salts, {[Cd(2,2′-dpdc)(tppp)(H₂O)]₂?·?2H₂O} _n (1), {[Pb(2,2′-dpdc)(pyphen)]₂} _n (2), and {[Pb(2,2′-dpdc)(dppz)]} _n (3) (H₂dpdc = 2,2′-diphenyldicarboxylic acid; tppp = 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol; pyphen?=?pyrazino[2,3-f]-[1,10]phenanthroline; and dppz = dipyrido[3,2-a:2′,3′-c]phenazine), are synthesized under hydrothermal conditions. These complexes are characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and photoluminescence. In 1, two 2,2′-dpdc ions bridge two Cd(II) ions to form an isolated cluster with Cd?···?Cd distance of 5.023(4)?Å. These clusters are further linked by intermolecular hydrogen bonds, yielding a 2-D supramolecular structure. Complex 2 contains two crystallographically independent Pb(II) ions in the asymmetric unit. Pb1 ions are bridged by 2,2′-dpdc anions to form a chain along the x-axis. Two Pb2 ions are coordinated by two 2,2′-dpdc anions and two pyphen ligands to form a cluster. These clusters are linked by π–π interactions to yield a 1-D supramolecular chain along the y-axis. In 3, neighboring Pb(II) atoms are bridged by 2,2′-dpdc anions to form a 1-D chain structure. Further, the chains are linked into a 3-D supramolecular network through aromatic π–π interactions.     

Exploratory syntheses,structures, and photoluminescent properties of three lead multi-dimensional frameworks

Three structurally diverse Pb^II coordination complexes, [Pb₃O(OH)(4-sphth)]₂(H₂O) (1), [Pb(3,5-Hdhb)]H₂O (2), and [Pb₃(4-nphth)₂(OH)₂] (3) (4-H₃sphth, 4-sulfophthalic acid; 3,5-H₂dhb, 3,5-dihydroxybenzoic acid; 4-H₂nphth, 4-nitrophthalic acid), were synthesized under hydrothermal conditions. X-ray diffraction analyses reveal that 1 is constructed from [Pb₄O₄] cubanes, based on which ladder-shaped structure is built via 4-H₃sphth bridge. This is the first Pb₄O₄-containing polymer. The Pb₂O₂ units in 2 are bridged by two parallel 3,5-HDHB ligands along the a-axis and two other parallel 3,5-HDHB ligands along the b-axis, forming a 3-D framework. For 3, the crystal structure is built up of a layer motif consisting of corner-sharing pyramidal Pb₃O units, which are linked through Pb corners to form a hexagonal unit. Each PbO₆ polyhedron is connected to three polyhedra (Pb₃O) via sharing an edge (two μ ₃-oxygen atoms) and two faces (three μ ₃-oxygen atoms), thus yielding an infinite 2-D Pb–O–Pb (3,6-net) honeycomb layer. The luminescence of 1–3 demonstrates that they may be good candidates for luminescent materials.     

A new compound constructed from Keggin anions and Cu-5,6-diamino-1,10-phenanthroline complexes: synthesis,structure, and characterization

A new inorganic–organic hybrid based on polyoxometalate, [Cu₂(daphen)₂(H₂O)₄(PW₁₁W^VO₄₀)]?·?6H₂O (1) (daphen?=?5,6-diamino-1,10-phenanthroline), was synthesized hydrothermally and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, and thermal analysis. Single-crystal X-ray diffraction analysis reveals that in 1 the Keggin anion [PW₁₂O₄₀]^4? is tetradentate, linking four Cu(II)-daphen fragments with its four terminal oxygen atoms in a plane; Cu²⁺ is coordinated by two terminal oxygen atoms of two [PW₁₂O₄₀]^4? anions, two water molecules, and two nitrogen atoms of the phen ring of a daphen, forming a polymeric layer. The 3-D architecture of the compound is further formed via hydrogen bonds between these layers. The daphen is bidentate chelating and does not participate in formation of hydrogen bonds. Redox of 1 was examined.     

Hydrothermal synthesis,structure, and properties of lead(II)-based coordination compounds with R-isophthalic acid (R=OH,CH3)

Three new lead(II)-based coordination polymers, [Pb(5-OH-BDC)] _n ?·?nH₂O (1) (5-OH-BDC?=?5-hydroxyisophthalate), [Pb₂(5-CH₃-BDC)₂] _n (2), and [Pb₂(5-CH₃-BDC)₂(phen)₂] _n ?·?2nH₂O (3) (5-CH₃-BDC?=?5-methylisophthalate, phen?=?1,10-phenanthroline), have been hydrothermally synthesized, structurally determined by single-crystal X-ray diffraction, and characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Both 1 and 2 exhibit 2-D double-layer network structures, while 3 possesses 1-D chain structure bridged by 5-CH₃-BDC. The coordination sphere of Pb(II) in 1 is holodirected, whereas in 2 and 3 the spheres feature hemidirected structures. Fluorescence properties of 1–3 have been investigated in the crystalline state at room temperature.     

Synthesis,structures, catalytic,and anticancer activities of some coordination compounds involving two new triazole derivatives

Five N-heterocyclic carboxylate-based coordination complexes, [Co(L¹)₂(H₂O)₂]·2H₂O (1), [Cd(L¹)₂(H₂O)₂]·2H₂O (2), [Co(L²)(H₂O)₃] (3), [Ni(L²)(H₂O)₃] (4), and [Cu₂(L²)₂(H₂O)₂] (5), have been synthesized and characterized by elemental analysis, IR spectroscopy, Powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray crystallography, where HL¹ is 2-((5-amino-1H-1,2,4-triazol-3-yl)thio)acetic acid and H₂L² is 2-((5-amino-1-(carboxymethyl)-1H-1,2,4-triazol-3-yl)thio)acetic acid. In these complexes, the hydrogen bonds (H-bonds) play an important role in their packing structures. Complex 1 has nine H-bonds showing a 3-D sqc38 topology. Complex 2 has 17 H-bonds exhibiting a 3-D hxl network. Complexes 3 and 4 are isomorphic, both of which possess ten H-bonds to present a 3-D btc topology. Complex 5 with eight H-bonds forms a 2-D sq1 structure. In addition, complex 3 catalyzes the decolorization of methyl orange. Meanwhile, 1, 3, and 5 show certain anticancer activities to inhibit the growth of HepG2 cells.     

Hydrothermal synthesis,structure, and photoluminescence of four complexes based on 1H-imidazole-4,5-dicarboxylate or 1H-imidazole-2-carboxylate ligands

Four complexes, [Ag₄(bipy)₂(Himdc)₂(H₂O)₂] _n (1), [Ag(H₂imdc)] _n (2), [K(H₃imdc)(H₂imdc)(H₂O)₂] _n (3), and [Cu(Himc)₂] (4) (H₃imdc?=?1H-imidazole-4,5-dicarboxylic acid, H₂imc?=?1H-imidazole-2-carboxylic acid, and bipy?=?4,4′-bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis and elemental analysis. The obtained complexes exhibit different coordination structures; 1 contains a 2-D supramolecular layer based on two chains arraying uniformly in an ABAB manner. Compound 2 displays sawtooth-shaped 1-D chains extending to 2-D layers via hydrogen bond interactions. Compound 3 possesses a 3-D framework structure based on a 1-D chain via hydrogen bonding interactions. Compound 4 has a 3-D framework structure bearing a pcu-type topology. In addition, the photoluminescence for 1 has been investigated.     

Ruthenium(II)-Phthalocyaninate(2–): Darstellung und Eigenschaften von Acido(carbonyl)phthalocyaninato(2–)ruthenat(II), [Ru(X)(CO)Pc2−]− (X = Cl,Br, I,NCO, NCS,N3)

Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) (ⁿBu₄N)[Ru(OH)₂Pc^2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H₂O)(CO)Pc^2?], which yields in tetrahydrofurane with excess (ⁿBu₄N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) isolated as red-violet, diamagnetic (ⁿBu₄N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc^2? ligand at approximately 15100 (B), 28300 (Q₁) und 33500 cm^?1 (Q₂), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N₃, NCO) 1948 cm^?1 (NCS), v(C? N) at 2208 cm^?1 (NCO), 2093 cm^?1 (NCS) and v(N? N) at 2030 cm^?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N₃), 504 (I), 499 (NCO), 498 cm^?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N₃), 336 (NCO) and 224 cm^?1 (NCS). Only v(Ru? I) is RR-enhanced.     

Preparation and characterization of four polymeric metal complexes based on the flexible ligand 1H-1,2,4-triazole-1-propionic acid in different conformations

Three 2-D layered coordination polymers with (4,4) topology, {[Cu(trzp)₂(H₂O)]·1.18H₂O} _n (1), {[Co(trzp)₂(H₂O)₂]·2H₂O} _n (2), and {[Cd(trzp)₂(H₂O)]·2H₂O} _n (3), have been synthesized with the flexible, bifunctional ligand 1H-1,2,4-triazole-1-propionate (trzp^?) as a two-connected bridge. In addition, a complicated 3-D MOF [Ag₃(trzp)₂(NO₃)] _n (4) has been obtained with the help of Ag?Ag interactions and trzp^? as a four-connected linker. Htrzp and 1–4 have been characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy. The structural analysis showed that Htrzp has a gauche conformation in the solid state. However, both gauche and trans conformers of trzp^? are observed in the crystals of 1; only one conformer of trzp^? exists in the other three compounds (trans conformation in 2 and 3, and gauche conformation in 4). The thermal behaviors of 1–4 have been examined by thermal gravimetric analysis under nitrogen, which revealed that metal cyanide salts M(CN) _n (M?=?Cu(II), Co(II), Cd(II), and Ag(I), n?=?1 or 2) may be an intermediate pyrolytic decomposition product of the corresponding compounds.