The supramolecular architecture of tris(naphthalene‐1,5‐diaminium) bis(5‐aminonaphthalen‐1‐aminium) octakis[hydrogen (5‐carboxypyridin‐3‐yl)phosphonate]

The asymmetric unit of the title compound, 3C₁₀H₁₂N₂²⁺·2C₁₀H₁₁N₂⁺·8C₆H₅NO₅P⁻, contains one and a half naphthalene‐1,5‐diaminium cations, in which the half‐molecule has inversion symmetry, one 5‐aminonaphthalen‐1‐aminium cation and four hydrogen (5‐carboxypyridin‐3‐yl)phosphonate anions. The crystal structure is layered and consists of hydrogen‐bonded anionic monolayers between which the cations are arranged. The acid monoanions are organized into one‐dimensional chains along the [101] direction via hydrogen bonds established between the phosphonate sites. (C)O—H...N_py hydrogen bonds (py is pyridine) crosslink the chains to form an undulating (010) monolayer. The cations serve both to balance the charge of the anionic network and to connect neighbouring layers via multiple hydrogen bonds to form a three‐dimensional supramolecular architecture.     

Copper(II) bis(4,4,4‐trifluoro‐1‐phenylbutane‐1,3‐dionate) complexes with pyridin‐2‐one, 3‐hydroxypyridine and 3‐hydroxypyridin‐2‐one ligands: molecular structures and hydrogen‐bonded networks

Copper(II) bis(4,4,4‐trifluoro‐1‐phenylbutane‐1,3‐dionate) complexes with pyridin‐2‐one (pyon), 3‐hydroxypyridine (hpy) and 3‐hydroxypyridin‐2‐one (hpyon) were prepared and the solid‐state structures of (pyridin‐2‐one‐κO )bis(4,4,4‐trifluoro‐3‐oxo‐1‐phenylbutan‐1‐olato‐κ²O ,O ′)copper(II), [Cu(C₁₀H₆F₃O₂)₂(C₅H₅NO)] or [Cu(tfpb‐κ²O ,O ′)₂(pyon‐κO )], (I), bis(pyridin‐3‐ol‐κO )bis(4,4,4‐trifluoro‐3‐oxo‐1‐phenylbutan‐1‐olato‐κ²O ,O ′)copper(II), [Cu(C₁₀H₆F₃O₂)₂(C₅H₅NO)₂] or [Cu(tfpb‐κ²O ,O ′)₂(hpy‐κO )₂], (II), and bis(3‐hydroxypyridin‐2‐one‐κO )bis(4,4,4‐trifluoro‐3‐oxo‐1‐phenylbutan‐1‐olato‐κ²O ,O ′)copper(II), [Cu(C₁₀H₆F₃O₂)₂(C₅H₅NO₂)₂] or [Cu(tfpb‐κ²O ,O ′)₂(hpyon‐κO )₂], (III), were determined by single‐crystal X‐ray analysis. The coordination of the metal centre is square pyramidal and displays a rare example of a mutual cis arrangement of the β‐diketonate ligands in (I) and a trans‐octahedral arrangement in (II) and (III). Complex (II) presents the first crystallographic evidence of κO‐monodentate hpy ligation to the transition metal enabling the pyridine N atom to participate in a two‐dimensional hydrogen‐bonded network through O—H…N interactions, forming a graph‐set motif R ₂²(7) through a C—H…O interaction. Complex (III) presents the first crystallographic evidence of monodentate coordination of the neutral hpyon ligand to a metal centre and a two‐dimensional hydrogen‐bonded network is formed through N—H…O interactions facilitated by C—H…O interactions, forming the graph‐set motifs R ₂²(8) and R ₂²(7).     

Tetraaquabis(d‐camphor‐10‐sulfonato)calcium(II)

The structure of the title compound, [Ca(C₁₀H₁₅O₄S)₂(H₂O)₄], is the first example in which two d ‐camphor‐10‐sulfonate anions are coordinated to a metal ion, in this case with direct Ca—O bonding. The molecule has crystallographically imposed twofold symmetry with the Ca atom on the twofold axis. Hydrogen bonds are formed between the coordinated water molecules and the O atoms of the SO₃⁻ groups of adjacent molecules, leading to the formation of a two‐dimensional layered network. The compound displays sharp wavelength‐selective transparency in the UV–visible spectrum, offering the potential for application as an optical filter.     

Synthesis,crystal structures and luminescence properties of seven mononuclear zinc(II), cadmium(II), cobalt(II) and nickel(II) complexes with 5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole

Due to their versatile coordination modes and metal‐binding conformations, triazolyl ligands can provide a wide range of possibilities for the construction of supramolecular structures. Seven mononuclear transition metal complexes with different structural forms, namely aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(H₂O)], (I), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]bis(nitrato‐κO )zinc(II), [Zn(NO₃)₂(C₁₄H₁₂N₄)₂], (II), bis(methanol‐κO )bis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(CH₄O)₂], (III), diiodidobis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]cadmium(II), [CdI₂(C₁₄H₁₂N₄)₂], (IV), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]bis(nitrato‐κO )cadmium(II), [Cd(NO₃)₂(C₁₄H₁₂N₄)₂], (V), aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]cobalt(II), [Co(C₁₄H₁₁N₄)₂(H₂O)], (VI), and diaquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]nickel(II), [Ni(C₁₄H₁₁N₄)₂(H₂O)₂], (VII), have been prepared by the reaction of transition metal salts (Zn^II, Cd^II, Co^II and Ni^II) with 3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole (pymphtzH) under either ambient or hydrothermal conditions. These compounds have been characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. All the complexes form three‐dimensional supramolecular structures through hydrogen bonds or through π–π stacking interactions between the centroids of the pyridyl or arene rings. The pymphtzH and pymphtz⁻ entities act as bidentate coordinating ligands in each structure. Moreover, all the pyridyl N atoms are coordinated to metal atoms (Zn, Cd, Co or Ni). The N atom in the 4‐position of the triazole group is coordinated to the Zn and Cd atoms in the crystal structures of (II), (IV) and (V), while the N atom in the 1‐position of the triazolate group is coordinated to the Zn, Co and Ni atoms in (I), (III), (VI) and (VII).     

A novel one‐dimensional double‐chain‐like ZnII coordination polymer: poly[bis(1‐benzyl‐1H‐imidazole‐κN3)tris(μ‐cyanido‐κ2C:N)(cyanido‐κC)disilver(I)zinc(II)]

One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous Zn^II coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like Zn^II coordination polymer, [Ag₂Zn(CN)₄(C₁₀H₁₀N₂)₂]_n, presents a one‐dimensional linear coordination polymer structure in which Zn^II ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each Zn^II ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated Zn^II ion. Interestingly, there are strong intermolecular Ag^I…Ag^I interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by Ag^I…Ag^I interactions between adjacent double chains. The photoluminescence properties have been studied.     

5‐n‐Butylpyridine‐2‐carboxylate–copper(II) and –iron(III) complexes

In trans‐bis(5‐n‐butyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­bis­(methanol‐κO)copper(II), [Cu(C₁₀H₁₂NO₂)₂(CH₄O)₂], the Cu atom lies on a centre of symmetry and has a distorted octahedral coordination. The Cu—O(methanol) bond length in the axial direction is 2.596 (3) Å, which is much longer than the Cu—­O(carboxylate) and Cu—N distances in the equatorial plane [1.952 (2) and 1.977 (2) Å, respectively]. In mer‐tris(5‐n‐bu­tyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­iron(III), [Fe(C₁₀H₁₂NO₂)₃], the Fe atom also has a distorted octahedral geometry, with Fe—O and Fe—N bond‐length ranges of 1.949 (4)–1.970 (4) and 2.116 (5)–2.161 (5) Å, respectively. Both crystals are stabilized by stacking interactions of the 5‐n‐butyl­pyridine‐2‐carboxyl­ate ligand, although hydrogen bonds also contribute to the stabilization of the copper(II) complex.     

Ni(II) and Pd(II) complexes bearing benzocyclohexane–ketoarylimine for copolymerization of norbornene with 5‐norbornene‐2‐carboxylic ester

A serial of late transition metal complexes, which bearing Benzocyclohexane–ketoarylimine ligand and named as Mt(benzocyclohexane–ketoarylimino)₂ {Mt(bchkai)₂: Mt=Ni or Pd; bchkai=C₁₀H₈(O)CN(Ar)CH₃; Ar=naphthyl or fluoryl}, have been synthesized and characterized. The molecular structures of the ligands and nickel complex have been confirmed by X‐ray single‐crystal analyses. The nickel complexes exhibited very high activity up to 2.7 × 10⁵ g_polymer/mol_Ni·h and palladium complexes showed high activity up to 2.3 × 10⁵ g_polymer/mol_Pd·h for norbornene (NB) homo‐polymerization with tris(pentafluorophenyl)borane as cocatalyst. The four complexes were effective for copolymerization of NB and 5‐norbornene‐2‐carboxylic acid methyl ester (NB‐COOCH₃) in relatively high activities (0.1–2.4 × 10⁵ g_polymer/mol_Mt·h) and produced the addition‐type copolymers with relatively high molecular weights (0.5 × 10⁵–1.2 × 10⁵ g/mol) as well as narrow molecular weight distributions (PDI < 2 for all polymers). Influences of the metals and comonomer feed content on the polymerization activity as well as on the incorporation rates (20.9–42.6%) were investigated. The achieved NB/NB‐COOCH₃ copolymers were confirmed to be noncrystalline, exhibited good thermal stability (T_d > 400°C) and showed good solubility in common organic solvents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

(S)‐5‐Benzylimidazolidine‐2,4‐dione monohydrate

The crystal structure of the title compound, C₁₀H₁₀N₂O₂·H₂O, also known as l ‐5‐benzylhydantoin monohydrate, is described in terms of two‐dimensional supramolecular arrays built up from infinite chains assembled via N—H...O and O—H...O hydrogen bonds among the organic molecules and solvent water molecules, with graph‐set R³₃(10)C(5)C²₂(6). The hydrogen‐bond network is reinforced by stacking of the layers through C—H...π interactions.     

Bis(adamantan‐1‐aminium) tetrachloridozincate(II) 18‐crown‐6 monohydrate clathrate

The structure of the title compound [systematic name: bis(adamantan‐1‐aminium) tetrachloridozincate(II)–1,4,7,10,13,16‐hexaoxacyclooctadecane–water (1/1/1)], (C₁₀H₁₈N)₂[ZnCl₄]·C₁₂H₂₄O₆·H₂O, consists of supramolecular rotator–stator assemblies and ribbons of hydrogen bonds parallel to [010]. The assemblies are composed of one protonated adamantan‐1‐aminium cation and one crown ether molecule (1,4,7,10,13,16‐hexaoxacyclooctadecane) to give an overall [(C₁₀H₁₈N)(18‐crown‐6)]⁺ cation. The –NH₃⁺ group of the cation nests in the crown and links to the crown‐ether O atoms through N—H...O hydrogen bonds. The 18‐crown‐6 ring adopts a pseudo‐C_3v conformation. The second adamantan‐1‐aminium forms part of ribbons of adamantan‐1‐aminium–water–tetrachloridozincate units which are interconnected by O—H...Cl, N—H...O and N—H...Cl hydrogen bonds via three different continuous rings with R₅⁴(12), R₄³(10) and R₃³(8) motifs.     

Two 17‐hydroxy‐9(10→5)‐abeo‐estr‐4‐ene‐3,10‐diones

(5S,9S,17S)‐17‐Hydroxy‐9(10→5)‐abeo‐estr‐4‐ene‐3,10‐dione, C₁₈H₂₆O₃, (II), and (5R,9R,17S)‐17‐hydroxy‐9(10→5)‐abeo‐estr‐4‐ene‐3,10‐dione, C₁₈H₂₆O₃, (III), are equimolecular products of the Fe^II‐induced transposition of 10β‐hydro­peroxy‐17β‐hydroxyestr‐4‐en‐3‐one, (I). With respect to reagent mol­ecules, the configuration at C9 is retained for (II) while it is inverted in (III). The conformations of the five‐ and six‐membered rings are compared.     

Polymer electrolyte membranes by in situ polymerization of poly(ethylene carbonate‐co‐ethylene oxide) macromonomers in blends with poly(vinylidene fluoride‐co‐hexafluoropropylene)

Salt‐containing membranes based on polymethacrylates having poly(ethylene carbonate‐co‐ethylene oxide) side chains, as well as their blends with poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP), have been studied. Self‐supportive ion conductive membranes were prepared by casting films of methacrylate functional poly(ethylene carbonate‐co‐ethylene oxide) macromonomers containing lithium bis(trifluorosulfonyl)imide (LiTFSI) salt, followed by irradiation with UV‐light to polymerize the methacrylate units in situ. Homogenous electrolyte membranes based on the polymerized macromonomers showed a conductivity of 6.3 × 10^?6 S cm^?1 at 20 °C. The preparation of polymer blends, by the addition of PVDF‐HFP to the electrolytes, was found to greatly improve the mechanical properties. However, the addition led to an increase of the glass transition temperature (T_g) of the ion conductive phase by ～5 °C. The conductivity of the blend membranes was thus lower in relation to the corresponding homogeneous polymer electrolytes, and 2.5 × 10^?6 S cm^?1 was recorded for a membrane containing 10 wt % PVDF‐HFP at 20 °C. Increasing the salt concentration in the blend membranes was found to increase the T_g of the ion conductive component and decrease the propensity for the crystallization of the PVDF‐HFP component. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 79–90, 2007     

Properties of the Magnesium(II) and Calcium(II) Complexes of 5‐ and 6‐Uracilmethylphosphonate (5 Umpa2– and 6 Umpa2–) in Aqueous Solution

The stability constants of the 1 : 1 complexes formed between Mg²⁺ or Ca²⁺ and 5 Umpa^2– or 6 Umpa^2– were determined by potentiometric pH titrations in aqueous solution (25 °C; I = 0.1 M, NaNO₃). Based on previously established log K^M_M(R‐PO3) versus pK^H_H(R‐PO3) straight‐line plots (M²⁺ = Mg²⁺ or Ca²⁺; R‐PO₃^2– = simple phosphate monoester or phosphonate ligands where R is a non‐interacting residue), it is shown that the Mg(5 Umpa), Ca(5 Umpa), Mg(6 Umpa) and Ca(6 Umpa) complexes have the stability expected on the basis of the basicity of the phosphonate group in 5 Umpa^2– and 6 Umpa^2–. This means, these ligands may be considered as simple analogues of nucleotides, e. g. of uridine 5′‐monophosphate. In the higher pH range deprotonation of the uracil residue in the M(5 Umpa) and M(6 Umpa) complexes occurs and this leads to the negatively charged M(5 Umpa–H)^– and M(6 Umpa–H)^– species. Based on the comparison of various acidity constants it is shown that the M(5 Umpa) complexes are especially acidic; or to say it differently, the M(5 Umpa–H)^– species are especially stable. This increased stability is attributed to the formation of a seven‐membered chelate involving next to the phosphonate group also the carbonyl oxygen atom at C4 (after deprotonation of the (N3)H site). The formation degree of this chelated isomer reaches about 45% for the Mg(5 Umpa–H)^– and Ca(5 Umpa–H)^– species. No indication for chelate formation was observed for the M(6 Umpa–H)^– complexes.     

Calcium(II) meso‐2,3‐di­phenyl­succinate heptahydrate

The title compound, [Ca(C₁₆H₁₂O₄)(H₂O)₆]·H₂O, adopts a conformation about the central C—C bond that places the two carboxylate groups in an anti orientation. The crystal consists of layers of two‐dimensional arrays of 2,3‐di­phenyl­succinate dianions which are linked by bridging Ca²⁺ cations. The unit cell contains two Ca²⁺ cations in an unusual four‐membered Ca—O—Ca—O ring in which the bridging O atoms belong to water mol­ecules rather than carboxyl­ates, i.e. poly­[[[di‐μ‐aqua‐bis­[penta­aqua­calcium(II)]]‐μ‐(meso‐2,3‐di­phenyl­succinato‐O:O′)] succinate dihydrate].     

Palladium(II)‐Komplexe des 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ5‐[1,3,5]triphosphinins

Palladium(II) Complexes of 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ⁵‐[1,3,5]triphosphinine 1,1,3,3,5,5‐Hexakis(dimethylamino)‐1λ⁵‐3λ⁵‐5λ⁵‐[1,3,5]triphosphinine ( 5 ) reacts with (benzonitrile)₂PdCl₂ to give the chelate complex dichloro(dodeca‐N‐methyl‐1λ⁵,3λ⁵,5λ⁵‐1,3,5‐triphosphinine‐1,1,3,3,5,5‐hexaamin‐C²,C⁴)palladium ( 6 ). In a pyridine‐d₅ solution of 6 the complex dichloro(dodeca‐N‐methyl‐1λ⁵,3λ⁵,5λ⁵‐1,3,5‐triphosphinine‐1,1,3,3,5,5‐hexaamin‐C²)((²H₅)pyridine‐N)palladium ( 7 ) is formed. The solute 7 could not be isolated as a solid, because elimination of the solvent regenerates 6 quantitatively. Properties, nmr and ir spectra of 6 and 7 are reported. 6 is characterized by the results of an X‐ray structural analysis.     

Dispersion‐Force‐Assisted Disproportionation: A Stable Two‐Coordinate Copper(II) Complex

The synthesis of the first linear coordinated Cu^II complex Cu{N(SiMe₃)Dipp}₂ ( 1 Dipp=C₆H₅‐2,6Prⁱ₂) and its Cu^I counterpart [Cu{N(SiMe₃)Dipp}₂]^? ( 2 ) is described. The formation of 1 proceeds through a dispersion force‐driven disproportionation, and is the reaction product of a Cu^I halide and LiN(SiMe₃)Dipp in a non‐donor solvent. The synthesis of 2 is accomplished by preventing the disproportionation into 1 by using the complexing agent 15‐crown‐5. EPR spectroscopy of 1 provides the first detailed study of a two‐coordinate transition‐metal complex indicating strong covalency in the Cu?N bonds.     

Synthesis and properties of poly(1‐naphthylacetylene) and poly(9‐anthrylacetylene)

Polymerizations of 1‐naphthylacetylene (1‐NA) and 9‐anthrylacetylene (9‐AA) by various transition metal catalysts were studied, and properties of the polymers were clarified. 1‐NA polymerized with WCl₆‐based catalysts to offer dark purple polymers in good yield. Especially, a binary catalyst composed of WCl₆ and Ph₃Bi gave a polymer with high molecular weight (M_w = 140×10³) and sufficient solubility in common solvents. The use of Mo and Rh catalysts, in contrast, resulted in the formation of insoluble red poly(1‐NA)s. 9‐AA gave insoluble polymers by both WCl₆‐ and MoCl₅‐based catalysts in moderate to good yields. Copolymerization of 9‐AA with 1‐NA by WCl₆–Ph₃Bi provided a soluble copolymer which exhibited the largest third‐order nonlinear optical susceptibilities (χ⁽³⁾(−3ω; ω, ω, ω) = 40×10⁻¹²) among all the substituted polyacetylenes synthesized so far. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 277–282, 1999     

N‐Ethylpyridinium bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)nickelate

The title compound, (C₇H₁₀N)[Ni(C₃S₅)₂] or (Etpy)[Ni(dmit)₂] (where Etpy is the N‐ethyl­pyridinium cation, C₇H₁₀N⁺, and dmit is the 2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ate dianion, C₃S₅²⁻), crystallizes in the P space group with two mol­ecules in the asymmetric unit. The [Ni(dmit)₂]⁻ monoanion has a planar D_2h conformation, with the central Ni atom and the four coordinated S atoms forming an NiS₄ square plane. The six‐membered ring of the Etpy cation also shows good planarity, as expected. There are two main types of disorder in the two Etpy cations. Several short intermolecular interactions are present, such as S⋯S, Ni⋯S and Ni⋯Ni, which help to form the enhanced three‐dimensional structure of the crystal.     

Complexes of nickel(II) and copper(II) with 1,2,4‐triazole‐3‐carboxylic acid and of cobalt(III) with 3‐amino‐1,2,4‐triazole‐5‐carboxylic acid

Because of their versatile coordination modes and strong coordination ability for metals, triazole ligands can provide a wide range of possibilities for the construction of metal–organic frameworks. Three transition‐metal complexes, namely bis(μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato)‐κ³N ²,O :N ¹;κ³N ¹:N ²,O‐bis[triamminenickel(II)] tetrahydrate, [Ni₂(C₃HN₃O₂)₂(NH₃)₆]·4H₂O, (I), catena‐poly[[[diamminediaquacopper(II)]‐μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato‐κ³N ¹:N ⁴,O‐[diamminecopper(II)]‐μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato‐κ³N ⁴,O :N ¹] dihydrate], {[Cu₂(C₃HN₃O₂)₂(NH₃)₄(H₂O)₂]·2H₂O}_n , (II), (μ‐5‐amino‐1,2,4‐triazol‐1‐ide‐3‐carboxylato‐κ²N ¹:N ²)di‐μ‐hydroxido‐κ⁴O :O‐bis[triamminecobalt(III)] nitrate hydroxide trihydrate, [Co₂(C₃H₂N₄O₂)(OH)₂(NH₃)₆](NO₃)(OH)·3H₂O, (III), with different structural forms have been prepared by the reaction of transition metal salts, i.e. NiCl₂, CuCl₂ and Co(NO₃)₂, with 1,2,4‐triazole‐3‐carboxylic acid or 3‐amino‐1,2,4‐triazole‐5‐carboxylic acid hemihydrate in aqueous ammonia at room temperature. Compound (I) is a dinuclear complex. Extensive O—H…O, O—H…N and N—H…O hydrogen bonds and π–π stacking interactions between the centroids of the triazole rings contribute to the formation of the three‐dimensional supramolecular structure. Compound (II) exhibits a one‐dimensional chain structure, with O—H…O hydrogen bonds and weak O—H…N, N—H…O and C—H…O hydrogen bonds linking anions and lattice water molecules into the three‐dimensional supramolecular structure. Compared with compound (I), compound (III) is a structurally different dinuclear complex. Extensive N—H…O, N—H…N, O—H…N and O—H…O hydrogen bonding occurs in the structure, leading to the formation of the three‐dimensional supramolecular structure.     

Enhanced third‐order nonlinear optical properties determined in thin films using the Z‐scan technique: bis(μ‐4,4′‐oxydibenzoato)bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine)cobalt(II)]

π‐Conjugated organic materials exhibit high and tunable nonlinear optical (NLO) properties, and fast response times. 4′‐Phenyl‐2,2′:6′,2′′‐terpyridine (PTP) is an important N‐heterocyclic ligand involving π‐conjugated systems, however, studies concerning the third‐order NLO properties of terpyridine transition metal complexes are limited. The title binuclear terpyridine Co^II complex, bis(μ‐4,4′‐oxydibenzoato)‐κ³O,O′:O′′;κ³O′′:O,O′‐bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine‐κ³N,N′,N′′)cobalt(II)], [Co₂(C₁₄H₈O₅)₂(C₂₁H₁₅N₃)₂], (1), has been synthesized under hydrothermal conditions. In the crystal structure, each Co^II cation is surrounded by three N atoms of a PTP ligand and three O atoms, two from a bidentate and one from a symmetry‐related monodentate 4,4′‐oxydibenzoate (ODA²⁻) ligand, completing a distorted octahedral coordination geometry. Neighbouring [Co(PTP)]²⁺ units are bridged by ODA²⁻ ligands to form a ring‐like structure. The third‐order nonlinear optical (NLO) properties of (1) and PTP were determined in thin films using the Z‐scan technique. The title compound shows a strong third‐order NLO saturable absorption (SA), while PTP exhibits a third‐order NLO reverse saturable absorption (RSA). The absorptive coefficient β of (1) is −37.3 × 10⁻⁷ m W⁻¹, which is larger than that (8.96 × 10⁻⁷ m W⁻¹) of PTP. The third‐order NLO susceptibility χ⁽³⁾ values are calculated as 6.01 × 10⁻⁸ e.s.u. for (1) and 1.44 × 10⁻⁸ e.s.u. for PTP.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.