Inorganic Chemistry Communications (v.9, #9)

Contents List (iii-ix).

Incorporation of 4,7-diphenyl-1,10-phenathroline (Ph2phen) into monometallic complexes of the form [(Ph2phen)2M(dpp)]2+, where M = Os(II) or Ru(II) and dpp = 2,3- bis(2-pyridyl)pyrazine, leads to emissive chromophores that can be integrated into supramolecular assemblies. The redox and spectroscopic properties of the molecules are reported.Monometallic light absorbing complexes of the form [(Ph2phen)2M(dpp)]2+ (M = Os(II) or Ru(II), Ph2phen = 4,7-diphenyl-1,10-phenanthroline, dpp = 2,3-bis(2-pyridyl)pyrazine) have been synthesized. The coupling of Ph2phen to Ru and Os complexes with polyazine bridging ligands will allow for the incorporation of these chromophores into supramolecular assemblies. The spectroscopic, redox and photochemical properties were studied. The complexes exhibit overlapping 1MLCT (metal-to-ligand charge transfer) transitions in their electronic absorbance spectroscopy with lowest energy peaks at 444 nm and 494 nm for [(Ph2phen)2Ru(dpp)]2+ and [(Ph2phen)2Os(dpp)]2+, respectively. An intense 3MLCT absorption for the Os complex centered at ca. 650 nm is also observed. The redox properties show significantly different reversible one electron metal oxidations, E 1 / 2 ox = 1.39 V and 1.02 V vs. Ag/AgCl for the Ru and Os complexes, respectively. Each complex displays three reversible reductions based on each polyazine ligand. The photophysical properties show strong 3MLCT emissions centered at 697 and 800 nm for the Ru and Os complexes, respectively.
Keywords: Ruthenium complexes; Osmium complexes; 4,7-Diphenyl-1,10-phenanthroline; 2,3-Bis(2-pyridyl)pyrazine; Bridging ligand; Emission;

The self-assembly reaction of 4-hydroxy-2-mercapto-6-methylpyrimidine, KOH and di-n-butyltin dichloride in CH3OH and H2O (V/V = 1:1) under solvothermal conditions (150 °C) affords a novel one-dimensional infinite polymeric chain complex 1, which involves high centrosymmetric units containing centrosymmetric hydrolysis ladders and unhydrolyzed Bu2Sn(IV) moieties.The self-assembly reaction of 4-hydroxy-2-mercapto-6-methylpyrimidine, KOH and di-n-butyltin dichloride in CH3OH and H2O (V/V=1:1) under solvothermal conditions (150 °C) affords a novel one-dimensional infinite polymeric chain complex 1, which involves high centrosymmetric units containing centrosymmetric hydrolysis ladders and unhydrolyzed Bu2Sn(IV) moieties.
Keywords: Polymers; Self-assembly; Solvothermal synthesis; Organotin;

A new resorcinol-substituted trimethylethylenediamine ligand and copper(II) bromide afford an unusual mixed-valent Cu(II)2Cu(I) trimer in which CuBr 3 2 - anion acts as a bridging ligand between two Cu(II) centres; the results reveal limitations to a previously reported strategy for assembly of helical coordination polymers.Copper complexes of a new resorcinol-substituted trimethylethylenediamine ligand have been isolated and characterised. The results reveal limitations to the use chiral ligands with hydrogen bond donor groups located for intermolecular hydrogen bonding for the self-assembly of helical coordination polymers and include the X-ray crystal structure of an unusual mixed-valent Cu(II)2Cu(I) trimer in which CuBr 3 2 - anion acts as a bridging ligand between the two Cu(II) centres.
Keywords: Copper; Cuprous tribromide ligand; Phenolate bridging ligand; Supramolecular assembly; X-ray crystallography; EPR spectroscopy;

We report the synthesis of two new dinickel(II) complexes with iodide and bridging terephthalate (tp2−) dianionic co-ligands, namely [Ni2L]I4  · 3H2O and catena-poly[[{Ni2L(OH2)2}2(μ-endo-tp)](μ-exo-tp)](ClO4)4  · 4H2O, where L represents a bis(macrocyclic) ligand, 7,7′-(propane-1,3-diyl)bis{3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene}, and the elucidation of their structures by single crystal X-ray analysis.Two new dinickel(II) complexes with iodide and bridging terephthalate (tp2−) dianionic co-ligands, namely [Ni2L]I4  · 3H2O (1) and catena-poly[[{Ni2L(OH2)2}2 (μ-endo-tp)](μ-exo-tp)](ClO4)4  · 4H2O (2), where L represents the bis(macrocyclic) ligand 7,7′-(propane-1,3-diyl)bis{3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene}, have been synthesized and their structures determined by the single crystal X-ray analysis. In the form of an iodide salt, (1) adopts a half-opened clamshell. The crystal of (2) consists of one-dimensional cationic chains in which the tetranuclear units, [{Ni2L(OH2)2}2(μ-endo-tp)], are linked by exo-bridging terephthalate anions.
Keywords: Synthesis; Dinickel(II) complex; Bis(macrocycle); One-dimensional chain; Half-opened clamshell; Terephthalate;

A coordination polymer containing the d-block, s-block metal ions and NTA3− ligand, in which the unusual coordination mode of NTA3− ligand has been found for the first time, is constructed by self-complementary self-assembly process.The reaction of the flexible ligand nitrilotriacetate with Cu(acac)2 under hydrothermal condition gave a unique 3D coordination polymer, NaCuNTAH2O (NTA3−  = the anion of nitrilotriacetate). Na+ ion plays an important role in chargeable and structural complementarity in the construction of 3D coordination framework. The unusual coordination mode of NTA ligand has been found for the first time. The complex is an example of coordination polymer containing the d-block, s-block metal ions and NTA3− ligand generated by an unusual self-complementary self-assembly process.
Keywords: d-block metal ion; s-block metal ion; Flexible ligand; Nitrilotriacetic acid; Coordination framework;

A chiral nickel(II) complex anchors both left- and right-handed aqua-chloro supramolecular helices.Both left- and right-handed supramolecular aqua-chloro helices, formed by hydrogen bonding interactions, are anchored by a new chiral Schiff-base nickel complex [NiL] in the compound [NiL] · 2HCl · 7H2O (1) (see scheme 1 for L); The asymmetric unit in the crystal structure of compound 1 contains fourteen non-coordinated water molecules and four hydrochloric acid molecules. All water molecules and chloride anions, present in the crystal lattice of 1, are exclusively involved in hydrogen bonding interactions.
Keywords: Nickel–Schiff-base complex; Chirality; Crystal structure; Water–chloride interactions; Helical arrangement; Supramolecular chemistry;

Dinuclear EGTA-copper(II) chelates with imidazole as auxiliary ligand by Carolina Alarcón-Payer; Elena Bugella-Altamirano; Duane Choquesillo-Lazarte; Alfonso Castiñeiras; Josefa María González-Pérez; Juan Niclós-Gutiérrez (903-906).
In LCu(μ2-EGTA)CuL complexes (L = H2O, Him or en), the conformation of each half of EGTA and distance of the weak Cu–O(ether) bond can be related to the coordination number of the copper(II) atom, the influence of the Jahn–Teller effect and the number of N atoms among the four closest donors in the Cu(II) coordination polyhedronBy reaction of Cu2CO3(OH)2 and H4EGTA with or without imidazole, the compounds [Cu2(EGTA)(H2O)2] · 2H2O (1), [Cu2(EGTA)(Him)2] n (2) and [Cu2(EGTA)(Him)4] · 4H2O (3) have been prepared. The EGTA acts in a μ2-bridging mode, with each half being tripodal-tetradentate in mer-NO2  + O(ether, apical) or NO + O(carboxy, apical) + O(ether, apical) conformation for compounds 1 and 2 or 3 and [Cu2(EGTA)(en)2] · 4H2O (4), respectively, as expected from the number of N donor atoms (0 and 1 or 2) supplied by the auxiliary ligands. The Cu–O(ether) bond length increases in the series 1  <  2  <  3  <  4, mainly influenced by the coordination number (5 or 6) of the copper(II) atom, the influence of the Jahn–Teller effect on it, giving from 4 + 1 to 4 + 1 + 1 surroundings, and the number of N atoms (1 to 3) among the four closest donor of the Cu(II) atom.
Keywords: Copper(II); Imidazole; EGTA; Crystal structure; Ligand conformation; Mixed-ligand complex;

A new β-CD inclusion complex with a seven-membered ring ▪ bridged organocobaloxime by Xin Zhang; Yi-Zhi Li; Hong Yan; Jun Hu; Hui-Lan Chen (907-910).
X-ray structure and 1H NMR have been applied to characterize a novel seven-membered ring ▪ bridged organocobaloxime/β-CD inclusion complex, which has been formed in a β-CD induced debromination reaction.This work demonstrates that by providing a confined environment, the cyclodextrin binding promotes the debromination reaction of aqua-(4-bromobutyl)cobaloxime to form a novel seven membered ring aqua(O-tetramethylene-CHEL)cobaloxime, which is included in the β-CD cavity and could not be prepared in the absence of β-cyclodextrin.
Keywords: Cyclodextrin; Organocobaloxime; Inclusion complex; Cyclization reaction;

Syntheses and structures of two Zn(II) complexes with the pentadentate Schiff-base ligands by Xu-Xia Sun; Chuan-Min Qi; Shu-Lan Ma; Hai-Bo Huang; Wen-xiang Zhu; Ying-Chun Liu (911-914).
Two new Schiff-base complexes [Zn · H2L1  · Cl2] · 0.5CH3OH (1) and [Zn2  · L2  · Cl2  · (CH3OH)2] (2) have been synthesized and structurally characterized. They have divergent structures though only possessing different positional methyls. Zn(II) in 1 is five-coordinated while 2 contains one novel ZnN3O4 core and one ZnO2Cl2 core. The coordinated units in 1 and 2 are both forming infinite one-dimensional hydrogen bond chains.Two structurally divergent zinc complexes [Zn · H2L1  · Cl2] · 0.5CH3OH (1) and [Zn2  · L2  · Cl2  · (CH3OH)2] of the newly designed pentadentate H2N3O2 Schiff bases H2L1 and H2L2 have been synthesized and structurally characterized. 1 has one five-coordinated Zn(II) ion in a distorted square-pyramid while 2 contains one novel seven-coordinate ZnN3O4 core in a pentagonal bipyramid polyhedron and one ZnO2Cl2 core in a trigonal pyramidal geometry. The coordinated units in 1 and 2 are both linked by hydrogen bonds forming infinite one-dimensional zigzag chains.
Keywords: Zinc; Schiff base; Seven-coordinate complex; Crystal structure; One-dimensional chain;

Two 3D supramolecular architectures from zinc hydrogen aconitate 1D polymers by George E. Kostakis; Ebbe Nordlander; Nick Hadjiliadis; Matti Haukka; John C. Plakatouras (915-919).
3D supramolecular architectures are formed through H-bonding and stacking interactions from two new linear Zn(II) coordination polymers with bridging trans-aconitates and Lewis bases.The reaction of Zn(NO3)2  · 3(H2O) with trans-aconitic acid, in presence of chelating Lewis bases, leads to the formation of the 1D polymers [Zn(N–N)(LH)] ·  nH2O, where LH3  =  trans-aconitic acid, 1 : N–N = 1,10-phenanthroline (phen), n  = 1, 2 : N–N = 2,2′-bipyridine (bpy), n  = 2. 3D supramolecular assemblies are constructed through H-bonding and stacking interactions.
Keywords: Zinc(II); 1D polymer; 3D supramolecular architecture; H-bond; Stacking; Crystal structure;

Synthesis and superparamagnetic property of a Co–Cr Prussian blue analogue nanoparticles inside Nafion membrane by Wataru Kosaka; Masanori Tozawa; Kazuhito Hashimoto; Shin-ichi Ohkoshi (920-922).
A nanoparticle-type of cobalt hexacyanochromate, K 0.19 I Co II [ Cr III ( CN ) 6 ] 0.73 · 4.5 H 2 O (particle diameter = 8 ± 2 nm) is prepared in Nafion. The nanoparticles show the superparamagnetism with blocking temperature (T B) of 8.5 K and an anisotropy energy barrier of 190 K. Magnetic hysteresis loops are observed below T B, e.g. 1.2 kOe at 2 K.A nanoparticle-type of cobalt hexacyanochromate, K 0.19 I Co II [ Cr III ( CN ) 6 ] 0.73 · 4.5 H 2 O (particle diameter = 8 ± 2 nm) is prepared in Nafion. The nanoparticles show the superparamagnetism with blocking temperature (T B) of 8.5 K and an anisotropy energy barrier of 190 K. Magnetic hysteresis loops are observed below T B, e.g. 1.2 kOe at 2 K.
Keywords: Nanoparticles; Prussian blue analogue; Superparamagnetism; Blocking temperature; Nafion;

Cyano-bridged one-dimensional chain containing mixed-valent Ru2(II,III) dinuclear unit by Wei Liu; Emmanuel Ngwang Nfor; Yi-Zhi Li; Jing-Lin Zuo; Xiao-Zeng You (923-925).
A one-dimensional chain containing paramagnetic Ru2(II,III) dinuclear complex and tricyanometalate precursor, [Ru2(O2CtBu)4][(Tp)Fe(CN)3] (1), was synthesized and structurally characterized. Magnetic measurements indicate that there is antiferromagnetic interaction between Ru2 unit (s  = 3/2) and low-spin FeIII ion (s  = 1/2).Using tricyanometalate [(Tp)Fe(CN)3] (Tp  = hydrotris(pyrazolyl)borate) as building block, the 1-D chain polymer containing paramagnetic Ru2(II,III) dinuclear complex, [Ru2(O2CtBu)4][(Tp)Fe(CN)3] (1), was synthesized and its structure was determined. Magnetic measurements indicate that there is antiferromagnetic interaction between Ru2 units (s  = 3/2) and low-spin FeIII ions (s  = 1/2).
Keywords: Diruthenium; Cyanide; Chain complexes; Magnetic properties; Crystal structures;

Self-assembly of a 3-D porous solid based on a 1-D Ag(I) coordination polymer by Kai-Ju Wei; Yong-Shu Xie; Jia Ni; Min Zhang; Qing-Liang Liu (926-930).
A novel Ag(I) luminescent complex 1 was demonstrated based on a new luminescent bridging ligand 3,6-di(2,2′-dipyridylamino)-9-phenyl-carbazole. 1 forms a novel channel-cupped shape one dimensional coordination polymer, which further pack into 3D porous framework via π⋯π stacking and C–H⋯O interactions.A new Ag(I) complex [Ag(ddpapcz)(NO3)] n (CH3CN) n (1) was obtained based on a novel luminescent bridging ligand 3,6-di(2,2′-dipyridylamino)-9-phenyl-carbazole (ddpapcz). Single crystal X-ray analysis has revealed that complex 1 forms a novel channel-cupped shape one dimensional coordination polymer. These 1D coordination polymers further pack into 3D porous frameworks via π⋯π stacking interactions and C–H⋯O hydrogen bonds. Furthermore, the ligand and complex are luminescent in the solid state, with emission maxima in the visible light region (λ max  = 423 and 435 nm for ddpapcz and complex 1, respectively).
Keywords: Ag compound; Coordination polymer; Crystal structure;

Dimeric and polymeric 3,5-dimethylpyrazole containing copper(II)benzoate complexes are prepared and structurally characterized. The oxidation of 3,5-dimethylpyrazole is accomplished leading to the formation of N-O-O by oxidation of N–H bond. Dimeric and trimeric copper(II) complexes containing N–O–O unit are structurally characterized.Dimeric and polymeric 3,5-dimethylpyrazole containing copper(II)benzoate complexes are prepared and structurally characterized. The complexes on oxidation led to formation of N–O–O by oxidation of N–H bond.
Keywords: Copper(II)benzoate; 3,5-dimethylpyrazole; Co-ordination polymer; Oxidative reactions; Radical;

Dipolar ruthenium-ammine complexes [Ru(NH3)5(L+)]4+/3+ (L+  = 4,4′-bipyridinium ions) were evaluated as both electron-transfer mediators (amperometric type) and electron-accepting indicators (colorimetric type) for glucose sensors.Dipolar ruthenium-ammine complexes [Ru(NH3)5(L+)]4+/3+ (L+  = 4,4′-bipyridinium ions) possess the low redox potentials of 0.15–0.18 V vs. Ag/AgCl and the great rate constants of 5.7 × 106–1.7 × 107  M−1  s−1 for the electron-transfer reactions between the reduced form of glucose oxidase and [Ru(NH3)5(L+)]4+. The color immediately changes from colorless to blue when glucose is added to an aqueous mixture containing [Ru(NH3)5(L+)]4+ and the oxidized form of glucose oxidase. These dipolar ruthenium-ammine complexes are concluded to be useful for both amperometric and colorimetric glucose sensors.
Keywords: Dipolar ruthenium-ammine complexes; Electron-transfer mediators; Electron-accepting indicators; Glucose sensors; Glucose oxidase;

Luminescence spectrum of uranyl(V) in 2-propanol perchlorate solution by Robin Steudtner; Thuro Arnold; Kay Großmann; Gerhard Geipel; Vinzenz Brendler (939-941).
The luminescence spectrum of uranyl U(V) in aqueous perchlorate solution was detected for the first time at room temperature in the UV–V is region with a peak maxima at 440 nm and a fluorescence lifetime of 1.1 ± 0.021 μs using an excitation wavelength of 255 nm.The luminescence spectrum of uranyl U(V) in aqueous perchlorate solution was detected for the first time at room temperature in the UV–Vis region with a peak maxima at 440 nm and a fluorescence lifetime of 1.1 ± 0.021 μs using an excitation wavelength of 255 nm.
Keywords: U(V); Fluorescence; Absorption; Photoreduction; Fluorescence lifetime;

Organic/Inorganic cluster salt for non-doping pure red electroluminescent devices by Jianliang Sun; Xutang Tao; Yutao Chuai; Fuzhi Wang; Dechun Zou; Jiaxiang Yang; Yan Ren; Zhi Liu; Minhua Jiang (942-945).
The salt of the organic/[Zn4(SPh)10]2− cluster was synthesized and used as a rare host emitter in non-doped red OLEDs. The devices based on it emit in the red region with a maximum wavelength of 630 nm and the emission peak was so narrow that the full width at half maximum (FWHM) is only about 80 nm.We report the synthesis and structure of a salt (C16H19N2)2[Zn4(C6H5S)10] formed by linking [Zn4(SPh)10]2− cluster with dye molecule trans-4-(4-dimethylamino-styryl)-N-methyl-pyridinium and its luminescent properties as a host emitter in non-doped OLEDs. Devices consisted of ITO/PEDOT (3000 rpm)/DMAS–Zn (2000 rpm)/BCP (10 nm)/Alq3 (20 nm)/Mg:Ag (10:1, mass ratio, 150 nm)/Ag (10 nm), emitted in the red region and the emission is centered at 630 nm. The full width at half maximum (FWHM) value of the emission peak is ∼80 nm.
Keywords: Clusters; Crystal structure; Electroluminescent;

Two metal complexes with the cis-P,P′-diphenyl-1,4-diphospha-cyclohexane (dpdpc) ligand are reported. The crystal structures of the distorted square planar Pd(II) and Pt(II) metal complexes, which show a small P–M–P bite angle are reported.The preparation and characterization of the novel Pd(II) and Pt(II) metal complexes with cis-P,P′-diphenyl-1,4-diphospha-cyclohexane (dpdpc) are described. The X-ray structures of [M(dpdpc)2]Cl2 (M = Pd, Pt) are also reported.
Keywords: Phosphine; Diphosphine; Platinum; Pladium; Metal complex; Crystal structure;

The hydrolysis of (thf)4Ba[(MeZn)2(PSitBu3)2] yields the novel oxygen-centered cage compound. The oxygen atom is in a square planar environment of zinc (green). The barium atoms (blue) complete the octahedral surrounding. Four faces are capped by phosphorus atoms (pink) and two edges by methyl groups (black).The reaction of (thf)4Ba[(MeZn)2(PSitBu3)2] (1) with water yields the cage compound bis[tris(THF)barium]dimethyltetrazinc tetrakis[tri(tert-butyl)silylphosphandiide] oxide, [(thf)3Ba]2Zn4(μ-Me)23-PSitBu3)46-O) (2). The hexa-coordinate oxygen atom is surrounded by four zinc atoms in a square planar fashion and by two barium atoms in a trans position. The methyl groups form three-center two-electron Ba–C–Zn bonds with Ba–C bond lengths of 307.7(5) pm. The metal atoms form a distorted octahedron with the tri(tert-butyl)silylphosphandiide ligands above BaZn2 faces.
Keywords: Barium; Zinc; Phosphanides; Cage compounds; Hydrolysis reactions;

With the ligand: N-(4-pyridylmethyl)benzimidazole having some flexibility and spacial hindrance, one-dimensional double helix with the chirality, ([AgL] · NO3) (1), which was synthesized by the diffusion reaction in a U-tube with H2O as diffusion mediate, is constructed by two single-helical chains with the same chirality through Van der Waals forces. But the compound 1 is racemic. And its luminescence is also discussed.With the ligand: N-(4-pyridylmethyl)benzimidazole having some flexibility and spacial hindrance, one-dimensional double helix with the chirality, ([AgL] · NO3) (1), which was synthesized by the diffusion reaction in a U-tube with H2O as diffusion mediate, is constructed by two single-helical chains with the same chirality through van der Waals forces. But the compound 1 is racemic.
Keywords: Silver(I) compound; Double helix; Luminescence;

Thiol end-capped one-dimensional platinum and palladium complexes by Deeb Taher; Bernhard Walfort; Gerard van Koten; Heinrich Lang (955-958).
The synthesis of acyl-thiol end-capped rigid-rod structured transition metal complexes of type [L n M ← NN → ML n ]2+ (L n M = Pd(PPh3)2(C6H4 ―C6H4 ―4-SC(O)Me, Pt[C6H2(CH2NMe2-2,6)2 ―4-SC(O)Me)]; NN = NC―C6H4 ―CN, NC5H4 ―CH=CH―C6H4 ―CH=CH―C5H4N) is described. The solid-state structure and the electrochemical behaviour of the latter species are discussed as well.The synthesis and characterisation of acyl-thiol end-capped homobimetallic rigid-rod structured molecules of type [(MeC(O)S―4-NCN)Pt ← NC―C6H4 ―CN → Pt(NCN―4-SC(O)Me)](OTf)2 (6, NCN = [C6H2(CH2NMe2-2,6)2]) and (MeC(O)S―4-C6H4 ―C6H4)(Ph3P)2Pd ← C5H4N―CH=CH―C6H4 ―CH=CH―C5H4N → Pd(PPh3)2(C6H4 ―C6H4 ―4-SC(O)Me)](OTf)2 (9) in which the metal fragments are spanned by π-conjugated organic connecting units is reported.

A dinuclear oxovanadium compound [V2O2(l-his)2(2,2′-bipy)2] ·  [C2H6O2  · (2,2′-bipy)] was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. X-band ESR spectroscopy of the sample indicated the existence of vanadium(IV) ions in the compound. The temperature dependent magnetic susceptibility data showed the presence of a ferromagnetic coupling between the two V(IV) ions in the range 4–180 K.A dinuclear oxovanadium compound [V2O2(l-his)2(2,2′-bipy)2] · [C2H6O2  · (2,2′-bipy)] was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. X-ray crystallography revealed that each vanadium center is six coordinated and adopts a distorted octahedral structure. IR spectroscopy, ESR spectrum and magnetic susceptibility data for this compound are given. X-band ESR spectroscopy of the sample indicated the existence of vanadium(IV) ions in the compound. The temperature dependent magnetic susceptibility data showed the presence of a ferromagnetic coupling between the two V(IV) ions in the range 4–180 K.
Keywords: Oxovanadium; Histidine; Hydrothermal synthesis; Crystal structure; Magnetic properties;

[Pb(endc)2(phen)] n is a nine-coordinated catenulate-like polymer, and [Pb(endc)(phen) · 3H2O]2 is a hepta-coordinated dimer; both of them hold hemidirected coordination geometries. To the best of our knowledge, [Pb(endc)2(phen)] n is the first hemidirected PbII coordinate with the coordination number of 9. For both compounds, the Pb–N, Pb–O(carboxyl) and Pb–O(carbonyl) bonds on the side away from lone pair of PbII are shorter than the rest of the same type, respectively; and these bonds become progressively longer, as they are arranged at the site nearer to the lone pair.Two novel PbII compounds [Pb(endc)2(phen)] n and [Pb(endc)(phen) · 3H2O]2 (endc and phen are the abbreviations of endonorbornene-cis-5,6-dicarboxylate anion and 1,10-phenanthroline, respectively) have been synthesized and characterized by single-crystal X-ray diffraction. [Pb(endc)2(phen)] n is a nine-coordinated catenulate-like polymer, and [Pb(endc)(phen) · 3H2O]2 is a hepta-coordinated dimer; both of them hold hemidirected coordination geometries. To the best of our knowledge, [Pb(endc)2(phen)] n is first hemidirected PbII coordinate with the coordination number of 9. For both compounds, the Pb–N, Pb–O(carboxyl) and Pb–O(carbonyl) bonds on the side away from lone pair of PbII are shorter than the rest of the same type, respectively; and these bonds become progressively longer, as they are arranged at the site nearer to the lone pair.
Keywords: Lead; Hemidirected coordinate; Coordination geometries; Coordination number;

A highly selective fluorescent chemosensor for Al3+ derivated from 8-hydroxyquinoline by Yonggang Zhao; Zhihua Lin; Haiping Liao; Chunying Duan; Qingjin Meng (966-968).
A novel two-branched amide-hydroxyquinoline fluorescent sensor exhibiting highly selective and affinitive for Al3+ over alkaline ions, alkaline earth ions and transition metal ions, has been designed and prepared.A novel fluorescent sensor was prepared and used as an ion-selective chemosensor for Al(III) via intramolecular excimer formation, from which a significant red shift along with an intensity enhancement of the excimer emission was observed in the presence of Al(III).
Keywords: Al3+; Fluorescent; Selectivity; Recognition;

A novel self-assembled layer consisting of water tetramers and nitrate anions has been observed in a cobalt complex. The water tetramers exist in an energetically less stable uudd configuration and are stabilized in the anionic host environments.A novel self-assembled layer consisting of water tetramers and nitrate anions has been observed in the [Co(1,10-phenanthroline)2(NO3)] · (NO3) · 4H2O complex. X-ray crystallography and FT-IR spectroscopy indicate that although the water tetramers exist in an energetically less stable uudd configuration, the anionic host environments may play an important role in the formation and stabilization of the water clusters.
Keywords: Water cluster; Crystal structure; Hydrogen bonds;

Two new oxalato-bridged dinuclear copper(II) complexes with di-2-pyridylamine: crystal structures, spectroscopic and magnetic properties by Sujittra Youngme; Achareeya Cheansirisomboon; Chanaiporn Danvirutai; Narongsak Chaichit; Chaveng Pakawatchai; Gerard A. van Albada; Jan Reedijk (973-977).
Two dinuclear Cu(II) complexes [Cu2(dpyam)2(μ-C2O4)(Cl)2] (1) and [Cu2(dpyam)2 (μ-C2O4)(CF3SO3)2] n (2) have been synthesized and their spectroscopic (IR, ligand field and EPR) and magnetic properties characterized. The structure of 1 is made up of the centrosymmetric dinuclear [{Cu(dpyam)(Cl)}2(μ-C2O4)] units, while 2 contains chains of the dimeric [Cu2(dpyam)2(μ-C2O4)(CF3SO3)2] units linked by the triflate anions. The two copper atoms in both compounds are linked through a bis-didentate oxalato group leading to a metal–metal separation of 5.526(1) and 5.228(3) Å. The stereochemistry of the Cu(II) chromophore in 1 is approximately square pyramidal, while compound 2 displays an elongated octahedral Cu(II) environment. The magnetic susceptibility measurements, measured from 5 to 350 K, revealed a very strong antiferromagnetic interaction between the Cu(II) atoms with a singlet–triplet energy gap (J) of −274 and −342 cm−1, for 1 and 2, respectively, in agreement with the coplanarity of the magnetic orbitals.Two dinuclear Cu(II) complexes of formula [Cu2(dpyam)2(μ-C2O4)(Cl)2] (1) and [Cu2(dpyam)2(μ-C2O4)(CF3SO3)2] n (2) (dpyam = di-2-pyridylamine) have been synthesized and their spectroscopic and magnetic properties characterized. The structure of 1 is made up of the centrosymmetric dinuclear [{Cu(dpyam)(Cl)}2(μ-C2O4)] units, while 2 contains chains of the dimeric [Cu2(dpyam)2(μ-C2O4)(CF3SO3)2] units linked by the triflate anions. The two copper atoms in both compounds are linked through a bis-didentate oxalato group leading to a metal–metal separation of 5.526(1) and 5.228(3) Å. The stereochemistry of the Cu(II) chromophore in 1 is approximately square pyramidal, while compound 2 displays an elongated octahedral Cu(II) environment. The IR, ligand field and EPR measurements are in agreement with the structures found. The magnetic susceptibility measurements, measured from 5 to 350 K, revealed a very strong antiferromagnetic interaction between the Cu(II) atoms with a singlet–triplet energy gap (J) of −274 and −342 cm−1, for compounds 1 and2, respectively, in agreement with the coplanarity of the magnetic orbitals.
Keywords: Copper(II); Crystal structure; μ-oxalato bridges; Magnetic properties; EPR;