A 3D Polyoxometalate‐Based Framework Constructed from Ag/trz Metal‐Organic Ribbons and P2W18 Polyoxoanions: Synthesis,Structure and Electrochemical Properties

A Wells‐Dawson Polyoxometalate‐based hybrid, Ag₉(trz)₃(Htrz)₄ (H₂O)(P₂W₁₈O₆₂)·3H₂O ( 1 ) (Htrz = 1,2,4‐1H‐triazole) was hydrothermally synthesized through using trz ligand and silver nitrate in the presence of [P₂W₁₈O₆₂]^6– polyoxoanion. In the 3D framework structure of compound 1 , two kinds of wave‐like Ag/trz chains originated from trz ligands and silver cations are aggregated in a “2+1” mode by {Ag₂/trz} linkages to result in a 1D Ag/trz metal‐organic ribbon, which is further extended into a 3D framework structure by [P₂W₁₈O₆₂]^6– polyoxoanions through Ag‐O covalent bonds. Additionally, the electrochemical properties of compound 1 have also been investigated.     

Bis(1,10‐phenanthroline‐κ2N,N′)(squarato‐κO)copper(II) trihydrate

The title mononuclear [Cu(sq)(phen)₂]·3H₂O complex [sq is squarate (C₄O₄) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)] has been synthesized and the structure consists of a neutral mononuclear [Cu(sq)(phen)₂] unit and three solvate water mol­ecules. The Cu^II ion has distorted square‐pyramidal coordination geometry, comprised of one carboxyl­ate O atom from a monodentate squarate ligand and four N atoms from two chelating phen ligands. An extensive three‐dimensional network of OW—H⋯O/OW hydrogen bonds, face‐to‐face π–­π interactions between the 1,10‐phenanthroline aromatic rings and a weak π–ring interaction are responsible for crystal stabilization.     

Synthesis,structure and electrochemical behavior of an organic-inorganic hybrid compound based on Dawson-type polyoxometalates

An organic-inorganic hybrid compound constructed from Wells-Dawson polyanion clusters and metal-organic complex subunits, [Cu(phen)₃][Cu(phen)₂Cu(phen)₂(P₂W₁₈O₆₂)]·2H₂O (1) has been prepared hydrothermally and characterized by elemental analysis, IR, UV, cyclic voltammetry (CV) and single-crystal X-ray diffraction. Crystal structural analysis indicates that two terminal oxygen atoms of the Wells-Dawson polyanion located in the “belt” site coordinate with Cu²⁺. Three Cu ions have different coordination environments: Cu1 and Cu2 are five-coordinate, while Cu3 is six-coordinate. The bisupporting polyoxoanions [Cu(phen)₂Cu(phen)₂(P₂W₁₈O₆₂)]^2? are polymerized into a 1D chain by hydrogen bonding interactions, then the chains are stacked into a two-dimensional structure via offset, face-to-face, π ··· π stacking interactions. CV reveals that 1 exhibits three chemically-reversible processes.     

Intramolecular π–π stacking in diaquabis(2‐hydroxybenzoato‐κO)bis(1,10‐phenanthroline‐κ2N,N′)strontium(II)

In the title compound, [Sr(C₇H₅O₃)₂(C₁₂H₈N₂)₂(H₂O)₂], the Sr^II ion is located on a twofold rotation axis and assumes a distorted square‐antiprism SrN₄O₄ coordination geometry, formed by two phenanthroline (phen) ligands, two 2‐hydroxybenzoate anions and two water molecules. Within the mononuclear complex molecule, intramolecular π–π stacking is observed between nearly parallel coordinated phen ligands, while normal intermolecular π–π stacking occurs between parallel phen ligands of adjacent complex molecules. Classic O—H...O and weak C—H...O hydrogen bonding helps to stabilize the crystal structure.     

Two Organic–Inorganic Hybrid 3D {P5W30}‐Based Heteropolyoxotungstates with Transition‐Metal/Ln–Carboxylate–Ln Connectors

Two unique organic–inorganic hybrid polyoxometalates constructed from Preyssler‐type [Na(H₂O)P₅W₃₀O₁₁₀]^14? ({P₅W₃₀}) subunits and TM/Ln–carboxylate–Ln connectors (TM=transition metal, Ln=lanthanide), KNa₇[{Sm₆Mn(μ‐H₂O)₂(OCH₂COO)₇(H₂O)₁₈}{Na(H₂O)P₅W₃₀O₁₁₀}] ? 22 H₂O ( 1 ) and K₄[{Sm₄Cu₂(gly)₂(ox)(H₂O)₂₄}{NaP₅W₃₀O₁₁₀}]Cl₂ ? 25 H₂O ( 2 ; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis‐NIR spectra, thermogravimetric analyses, power X‐ray diffraction, and single‐crystal X‐ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P₅W₃₀}, [Sm₂Mn(μ‐H₂O)₂(OCH₂COO)₂(H₂O)₅]⁴⁺, and [Sm₄(OCH₂COO)₅ (H₂O)₁₃]²⁺, whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P₅W₃₀}, [SmCu(gly)(H₂O)₈]⁴⁺, and [Sm₂(ox)(H₂O)₈]⁴⁺. To our knowledge, 1 and 2 are the first 3D frameworks that contain {P₅W₃₀} units and TM/Ln–carboxylate–Ln connectors. The fluorescent properties of 1 and 2 have been investigated.     

Two Self‐assembled Water Clusters Stabilized by Cu‐containing Compounds Based on MoO42–

Two copper‐containing compounds based on MoO₄^2–, [Cu₄(phen)₄(μ₂‐OH)₂(μ₃‐OH)₂(H₂O)₂][MoO₄]₂ · 10H₂O ( 1 ) and [Cu(phen)₂Mo₂O₇(phen)] · 8H₂O ( 2 ) (phen = 1,10‐phenanthroline), were hydrothermally synthesized. In the crystal lattices of 1 and 2 , discrete octameric water cycles and 2D layer water clusters were observed. The cyclic water octamer clusters exist stably in the channels constructed by [Cu₄(phen)₄(OH)₄(H₂O)₂]²⁺ and MoO₄^2– by hydrogen bonds in 1 at low temperature and 2D layer water clusters are formed by (H₂O)₁₆ units in 2 .     

Decorated Dawson Anion by Two Different Complex Fragments of Phenanthroline and Isonicotinic Acid: Synthesis and Properties

An unreported inorganic–organic hybrid compound [{Cu₂(phen)₂(ina)₂(H₂O)}{Cu(phen)₂}(H₂P₂W₁₈O₆₂)]·10H₂O(1) (phen = 1,10-phenanthroline, ina = isonicotinate anion) was hydrothermally synthesized and characterized with elemental analysis, IR spectroscopy, thermal analysis, luminescent spectroscopy, UV/Vis diffuse reflection spectroscopy, magnetic measurement. The crystal structure was determined with X-ray single-crystal diffraction. [Cu(phen)₂]²⁺and [Cu₂(phen)₂(ina)₂(H₂O)]²⁺ units are grafted on the Dawson anion [P₂W₁₈O₆₂]^6? via the terminal oxygen atoms of two WO₆ octahedra. In [Cu₂(phen)₂(ina)₂(H₂O)]²⁺ unit Cu²⁺ ions displays a square-pyramidal geometry, and in [Cu(phen)₂]²⁺ unit the geometry of Cu²⁺ ion is more close to triangle bipyramidal geometry including a terminal oxygen atom. Hydrogen bonds exist between the decorated Dawson anions and water molecules. The compound 1 has a narrow band gap of 2.05 eV and strong emission at 437 nm. Variable-temperature magnetic measurement of 1 shows a typical antiferromagnetic interaction in the 2–300 K temperature range.     

Di­aqua­bis(1,10‐phenanthroline‐κ2N,N′)­manganese(II) thiodiglycolate bis(1,10‐phenanthroline‐κ2N,N′)(thiodiglycolato‐κ2O,O′)­manganese(II) tridecahydrate

The title compound, [Mn(C₁₂H₈N₂)₂(H₂O)₂](C₄H₄O₄S)·[Mn(C₄H₄O₄S)(C₁₂H₈N₂)₂]·13H₂O, contains one dianion of thio­diglycolic acid (tdga²⁻) and two independent man­ganese(II) moieties, viz. [Mn(phen)₂(H₂O)₂]²⁺ and [Mn(tdga)(phen)₂], where phen is 1,10‐phenanthroline. The Mn^II atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga²⁻ dianion is hydrogen bonded to an [Mn(phen)₂(H₂O)₂]²⁺ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water mol­ecules.     

A novel inorganic-organic hybrid based on a Wells–Dawson polyanion containing two types of organic fragments

A new inorganic-organic hybrid, [Zn(phen)₂(ppy)][{Zn(phen)₂}{Zn(phen)₂(H₂O)}{P₂W₁₈O₆₂}]?·?2H₂O (phen?=?1,10′-phenanthroline, ppy?=?2-(5-phenylpyridin-2-yl)pyridine) (1), by using pre-prepared Wells–Dawson salt α-K₆P₂W₁₈O₆₂?·?15H₂O as precursor, has been synthesized under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray diffraction, elemental analyses, IR spectrum and cyclic voltammetry. Yellow crystals crystallized in the monoclinic space group P2 (1)/c with a?=?16.2450(11)?Å, b?=?17.0918(11)?Å, c?=?43.640(3)?Å, β?=?92.0060(10)°, V?=?12109.4(14)?ų, Z?=?4. The title compound represents a novel zero-dimensional structure based on bisupporting Wells–Dawson POM: one terminal oxygen atom located in the “belt” site and another located in the “cap” site of the same hemisphere of the polyanion are coordinated by Zn²⁺ cations. Compound 1 also contains the isolated secondary metal complex [Zn(phen)₂(ppy)]²⁺ with two different organic ligands phen and ppy.     

三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能

在水热条件下,通过Wells-Dawson型多酸[As_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(4-吡啶基)-1H-四氮唑(4-ptz)的反应,在同一反应釜中合成出2个结构完全不同的、都包含三核铜簇的多酸基化合物[Cu3(4-ptz)4(H_2O)7(As_2W_(18)O_(62))]·42H_2O(1)和[Cu3(4-ptz)5(H_2O)5(As_2W_(18)O_(62))]·47H_2O(2);当我们以另一种Wells-Dawson型多酸[P_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(3-吡啶基)-1H-四氮唑(3-ptz)反应,获得了另一种多酸基三核铜簇化合物[Cu3(3-ptz)4(H_2O)8(P_2W_(18)O_(62))]·33H_2O(3)。X射线单晶衍射结果表明,化合物1为多酸单支撑三核铜簇的悬臂式结构,化合物2的多阴离子被三核铜簇交替连接形成一维链式结构,而化合物3为多阴离子和三核铜簇形成的孤立结构。吡啶-四氮唑类配体(3-ptz和4-ptz)是形成化合物1~3中三核铜簇的重要结构因素。同时,研究了3个化合物的电化学以及光催化性能。     

μ‐Acetato‐μ‐aqua‐μ‐hydroxido‐bis[(1,10‐phenanthroline)copper(II)] dinitrate monohydrate

The triply bridged title dinuclear copper(II) compound, [Cu₂(C₂H₃O₂)(OH)(C₁₂H₈N₂)₂(H₂O)](NO₃)₂·H₂O, (I), consists of a [Cu₂(μ₂‐CH₃COO)(μ₂‐OH)(phen)₂(μ₂‐OH₂)]²⁺ cation (phen is 1,10‐phenanthroline), two uncoordinated nitrate anions and one water molecule. The title cation contains a distorted square‐pyramidal arrangement around each metal centre with a CuN₂O₃ chromophore. In the dinuclear unit, both Cu^II ions are linked through a hydroxide bridge and a triatomic bridging carboxylate group, and at the axial positions through a water molecule. The phenanthroline groups in neighbouring dinuclear units interdigitate along the [010] direction, generating several π–π contacts which give rise to planar arrays parallel to (001). These are in turn connected by hydrogen bonds involving the aqua and hydroxide groups as donors with the nitrate anions as acceptors. Comparisons are made with isostructural compounds having similar cationic units but different counter‐ions; the role of hydrogen bonding in the overall three‐dimensional structure and its ultimate effect on the cell dimensions are discussed.     

Three Dicyanidometallate(I)‐based Complexes Incorporating Hydrogen‐bonding, π–π Packing and d10–d10 Interactions with Auxiliary 2,2′‐Bipyridyl‐like Ligands

To investigate the influence of the non‐covalent interactions, such as hydrogen‐bonding, π–π packing and d¹⁰–d¹⁰ interactions in the supramolecular motifs, three cyanido‐bridged heterobimetallic discrete complexes {Mn(bipy)₂(H₂O)[Ag(CN)₂]}[Ag(CN)₂] ( 1 ), {Mn(phen)₂(H₂O)[Au(CN)₂]}₂[Au(CN)₂]₂ · 4H₂O ( 2 ), and {Cd(bipy)₂(H₂O)[Au(CN)₂]}[Au(CN)₂] ( 3 ) (bipy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline), which are based on dicyanidometallate(I) groups with 1:2 stoichiometry of metal ions and 2,2′‐bipyridyl‐like co‐ligands were synthesized and structurally characterized. In compound 1 , hydrogen bonding and π–π interactions governed the supramolecular contacts. In compound 2 , the incorporation of aurophilic, hydrogen bonding and π–π interactions result in a 3D supramolecular network. In compound 3 , hydrogen bonding and π–π stacking interactions result in a 2D supramolecular layer. In the three complexes, hydrogen‐bonding, π–π packing and/or d¹⁰–d¹⁰ interactions can play important roles in increasing the dimensionality of supramolecular assemblies.     

A photochromic dinuclear compound: aquatetrakis(μ‐2,3‐diphenylprop‐2‐enoato)bis(2,3‐diphenylprop‐2‐enoato)ethanolbis(1,10‐phenanthroline)dilanthanum(III)

The title dinuclear complex, (aqua‐1κO)tetrakis(μ‐2,3‐diphenylprop‐2‐enoato‐1:2κ²O:O′)bis(2,3‐diphenylprop‐2‐enoato)‐1κO;2κO‐(ethanol‐2κO)bis(1,10‐phenanthroline)‐1κ²N,N′;2κ²N,N′‐dilanthanum(III), [La₂(C₁₅H₁₁O₂)₆(C₁₂H₈N₂)₂(C₂H₅OH)(H₂O)], contains two similar La^III centres with distorted [LaO₆N₂] bicapped triganol–prismatic coordination polyhedra formed by six phenylcinnamate (PCA⁻ or 2,3‐diphenylprop‐2‐enoate) ligands, two 1,10‐phenanthroline (phen) ligands, a coordinating ethanol molecule and a coordinating water molecule. The two metal centres are bridged by four μ‐PCA⁻ ligands, with the remaining two PCA⁻ ligands coordinated in a monodentate fashion. The noncoordinated carboxylate O atoms on the terminal PCA⁻ ligands form O—H...O hydrogen bonds with the coordinated solvent molecules. Each La centre is also coordinated by a bidentate phen ligand. The PCA⁻ ligands all adopt syn–syn orientations, with the two phenyl rings presenting dihedral angles of about 70°. The compound displays photochromic behaviour both in solution and in the solid state.     

Poly[aquaneodymium(III)‐μ5‐2‐oxido‐5‐sulfonatobenzoato]

The title compound, [Nd(C₇H₃O₆S)(H₂O)]_n or [Nd(SSA)(H₂O)]_n (H₃SSA is 5‐sulfosalicylic acid), was synthesized by the hydrothermal reaction of Nd₂O₃ with H₃SSA in water. The compound forms a three‐dimensional network in which the asymmetric unit contains one Nd^III atom, one SSA ligand and one coordinated water mol­ecule. The central Nd^III ion is eight‐coordinate, bonded to seven O atoms from five different SSA ligands [Nd—O = 2.405 (4)–2.612 (4) Å] and one aqua O atom [Nd—OW = 2.441 (4) Å].     

Monodentate Coordination of 4,4′‐Bipyridine Leading to a Supramolecular Network – Synthesis and Crystal Structure of [H2bpp][{Cu(Hbpy)2}{α‐HP2W18O62}]·4H2O

The new supramolecular compound [H₂bpp][{Cu(Hbpy)₂}{α‐HP₂W₁₈O₆₂}]·4H₂O ( 1 ) (bpy = 4,4′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane) was synthesized hydrothermally and characterized byelemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. In compound 1 , the cationic fragment [Cu(Hbpy)₂]⁺ connects to the Dawson anion through a coordinating Cu←O bond, and the copper atom is coordinated by another polyoxoanion through a weak covalent bond with a Cu1–O26 distance of 2.879(2) Å, forming a polymeric chain. The bpy ligand in [Cu(Hbpy)₂]⁺ adopts a monodentate coordination mode, the other nitrogen atom of the bpy ligand is protonated. The protonated Hbpy⁺ acts as hydrogen‐bond donor and constructs a two‐dimensional double‐sheet supramolecular network involving the one‐dimensional chains through the hydrogen bonds. The H₂bpp²⁺ ion connects twoα‐HP₂W₁₈O₆₂^6– clusters from two supramolecular networks through hydrogen bonds and creates a three‐dimensional supramolecular architecture. The thermal decomposition of 1 happens over a wide temperature range (450–800 °C), which indicates that it might include complicated oxidation–reduction processes.     

Anthraquinone‐2,6‐disulfonate as Versatile Ligand for the Synthesis of Hydrogen‐Bonded Supramolecules

The reactions of anthraquinone‐2,6‐disulfonic acid disodium salt (Na₂a‐2,6‐dad) with Cu^II, Mn^II, and Zn^II with 1,10‐phenanthroline (phen) or 2,2′‐dipyridyl (bipy) under hydrothermal conditions formed two or three‐dimensional supramolecules of stoichiometries [Cu(a‐2,6‐dad)(phen)(H₂O)₃](H₂O)₄ ( 1 ), [Mn(a‐2,6‐dad)(bipy)₂(H₂O)](H₂O)₂ ( 2 ), and [Zn(a‐2,6‐dad)(bipy)₂(H₂O)](H₂O)₂ ( 3 ), which were synthesized and characterized. The arrangement around each metal atom is distorted octahedral. The ligands in all the compounds are engaged in intermolecular hydrogen bonding leading to the formation of hydrogen‐bonded networks, the compounds show novel π–π stacking interactions. Photoluminescence measurements indicate that the compound [Zn(a‐2,6‐dad)(bipy)₂(H₂O)](H₂O)₂ ( 3 ) shows strong blue luminescence in the solid state at room temperature.     

A 3D Hybrid Praseodymium–Antimony–Oxochloride Compound: Single‐Crystal‐to‐Single‐Crystal Transformation and Photocatalytic Properties

A 3D organic–inorganic hybrid compound, (2‐MepyH)₃ [{Fe(1,10‐phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH) Cl_11.5}(TDC)_4.5({Pr₄Sb₁₂O₁₈(OH)Cl_9.5} Cl)] ? 3 (2‐Mepy) ? 28 H₂O ( 1 ; 2‐Mepy=2‐methylpyridine, 1,10‐phen=1,10‐phenanthroline, H₂TDC=thiophene‐2,5‐dicarboxylic acid), was hydrothermally synthesized and structurally characterized. Unusually, two kinds of high‐nuclearity clusters, namely [(Pr₄Sb₁₂O₁₈ (OH)Cl₁₁)(COO)₅]^5? and [(Pr₄Sb₁₂O₁₈ (OH)Cl₉)Cl(COO)₅]^4?, coexist in the structure of compound 1 ; two of the latter clusters are doubly bridged by two μ₂‐Cl^? moieties to form a new centrosymmetric dimeric cluster. An unprecedented spontaneous and reversible single‐crystal‐to‐single‐crystal transformation was observed, which simultaneously involved a notable organic‐ligand movement between the metal ions and an alteration of the bridging ion in the dimeric cluster, induced by guest‐release/re‐adsorption, thereby giving rise to the interconversion between compound 1 and the compound (2‐MepyH)₃[{Fe(1,10‐phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH)Cl_11.5}(TDC)₄({Pr₄Sb₁₂O₁₈Cl_10.5(TDC)_0.5(H₂O)_1.5}O_0.5)] ? 25 H₂O ( 1′ ). The mechanism of this transformation has also been discussed in great detail. Photocatalytic H₂‐evolution activity was observed for compound 1′ under UV light with Pt as a co‐catalyst and MeOH as a sacrificial electron donor.     

Crystal structure,shape analysis and bioactivity of new LiI,NaI and MgII complexes with 1,10‐phenanthroline and 2‐(3,4‐dichlorophenyl)acetic acid

Reactions of 1,10‐phenanthroline (phen) and 2‐(3,4‐dichlorophenyl)acetic acid (dcaH) with M_n(CO₃) (M = Li^I, Na^I and Mg^II; n = 1 and 2) in MeOH yield the mononuclear lithium complex aqua[2‐(3,4‐dichlorophenyl)acetato‐κO](1,10‐phenanthroline‐κ²N,N′)lithium(I), [Li(C₈H₅Cl₂O₂)(C₁₂H₈N₂)(H₂O)] or [Li(dca)(phen)(H₂O)] ( 1 ), the dinuclear sodium complex di‐μ‐aqua‐bis{[2‐(3,4‐dichlorophenyl)acetato‐κO](1,10‐phenanthroline‐κ²N,N′)sodium(I)}, [Na₂(C₈H₅Cl₂O₂)₂(C₁₂H₈N₂)₂(H₂O)₂] or [Na₂(dca)₂(phen)₂(H₂O)₂] ( 2 ), and the one‐dimensional chain magnesium complex catena‐poly[[[diaqua(1,10‐phenanthroline‐κ²N,N′)magnesium]‐μ‐2‐(3,4‐dichlorophenyl)acetato‐κ²O:O′] 2‐(3,4‐dichlorophenyl)acetate monohydrate], {[Mg(C₈H₅Cl₂O₂)(C₁₂H₈N₂)(H₂O)₂](C₈H₅Cl₂O₂)·H₂O}_n or {[Mg(dca)(phen)(H₂O)₂](dca)·H₂O}_n ( 3 ). In these complexes, phen binds via an N,N′‐chelate pocket, while the deprotonated dca^? ligands coordinate either in a monodentate (in 1 and 2 ) or bidentate (in 3 ) fashion. The remaining coordination sites around the metal ions are occupied by water molecules in all three complexes. Complex 1 crystallizes in the triclinic space group P with one molecule in the asymmetric unit. The Li⁺ ion adopts a four‐coordinated distorted seesaw geometry comprising an [N₂O₂] donor set. Complex 2 crystallizes in the triclinic space group P with half a molecule in the asymmetric unit, in which the Na⁺ ion adopts a five‐coordinated distorted spherical square‐pyramidal geometry, with an [N₂O₃] donor set. Complex 3 crystallizes in the orthorhombic space group P2₁2₁2₁, with one Mg²⁺ ion, one phen ligand, two dca^? ligands and three water molecules in the asymmetric unit. Both dcaH ligands are deprotonated, however, one dca^? anion is not coordinated, whereas the second dca^? anion coordinates in a bidentate fashion bridging two Mg²⁺ ions, resulting in a one‐dimensional chain structure for 3 . The Mg²⁺ ion adopts a distorted octahedral geometry, with an [N₂O₄] donor set. Complexes 1 – 3 were evaluated against urease and α‐glucosidase enzymes for their inhibition potential and were found to be inactive.     

Diaquabis(2,5‐dihydroxybenzoato‐κO)bis(1,10‐phenanthroline‐κ2N,N′)strontium(II) bis(1,10‐phenanthroline) tetrahydrate

The title compound, [Sr(C₇H₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₁₂H₈N₂·4H₂O, consists of an Sr^II complex, uncoordinated phenanthroline (phen) molecules and solvent water molecules. The Sr^II ion is located on a twofold axis and is coordinated by two phen ligands, two dihydroxybenzoate anions and two water molecules in a distorted tetragonal antiprismatic geometry. Partially overlapped arrangements exist between parallel coordinated and parallel uncoordinated phen rings; the face‐to‐face separations between the former (coordinated) and the latter (uncoordinated) rings are 3.436 (13) and 3.550 (14) Å, respectively. This difference suggests the effect of metal coordination on π–π stacking between phen rings.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.