Inorganic Chemistry Communications (v.11, #3)

Contents List (iii-x).

Towards a phosphorescent cyclometalated iridium complex containing a modified polymerizable acetylacetonato ligand by Marion Graf; Valeria Gancheva; Manuel Thesen; Hartmut Krüger; Peter Mayer; Karlheinz Sünkel (231-234).
The synthesis and the X-ray crystal structure of the cyclometalated iridium(III) complex [Ir(ppy)2(phC6-acac)] (1, ppy = 2-phenylpyridyl, phc6-acac = 11-(2,5-dibromo-4-hexyloxy-phenoxy)-undecane-2,4-dione) is presented. The emission spectrum of 1 exhibits this complex as a green-light-emitting compound.A convenient synthesis of the complex [Ir(ppy)2(phC6-acac)] (1, ppy = 2-phenylpyridyl, phC6-acac = 11-(2,5-dibromo-4-hexyloxy-phenoxy)-undecane-2,4-dione) from [{Ir(μ-Cl)(ppy)2}2], phC6-acacH and silver trifluoroacetate as the halide abstractor in refluxing acetone is described. The crystal and molecular structure of 1 was determined by X-ray crystallography.
Keywords: Iridium; Cyclometalated complex; Photoluminescence; Crystal structure;

Palladacycle complexes of (S)-4-iso-propyl-2-phenyl-2-oxazoline: Synthesis, crystal structures and catalytical methanolysis of pesticide by Hua-Min Li; Jian-Guo Su; Zhong-Lin Lu; Hoong-Kun Fun; Suchada Chantrapromma (235-238).
Two palladacycle compounds with chiral oxazoline backbone (1 and 2), which were synthesized and structurally characterized, showed high catalytic activity in the methanolysis of pesticide.Two pyridine coordinated cyclopalladated complexes: (S)-chloro{2-[2-(4-iso-propyl)oxazolinyl]phenyl-C,N}(4-R-pyridine)palladium(II) (R = H, 1, R = NMe2, 2), have been synthesized and structurally characterized. Both complexes show that the palladium atom displays the expected square planar coordination with the pyridine and oxazoline nitrogen atoms positioned trans to one another. These two palladacycles can effectively catalyze the methanolysis of pesticide fenitrothion with an acceleration above 106–107 folds compared to that of the methoxide-catalyzed background reaction at pH s s values of 10.80 and room temperature.
Keywords: Palladacycle; Crystal structure; Methanolysis; Phenyloxazoline;

Novel hexanuclear zinc(II) complex of 1,3,5-benzenemethyltriiminodiacetate by Yongmei Zhao; Shourong Zhu; Min Shao; Xiang He; Mingxing Li; Wencong Lu (239-242).
The titled cyclic dimer of a trinuclear zinc complex, {[Zn3(bmtac)(H2O)8] · 6H2O}2, based on the flexible 1,3,5-benzenemethyltriiminodiacetic acid (H6bmtac) ligand not only is the first reported crystal structure of complex of H6bmtac, but also is possibly one of the largest hexanuclear zinc(II) complex.A novel cyclic dimer of a trinuclear zinc complex, {[Zn3(bmtac)(H2O)8] · 6H2O}2, with very long Zn–Zn distances, was synthesized in aqueous solution by adopting a new type of flexible multicarboxylate ligand, H6bmtac (H6bmtac = 1,3,5-benzenemethyltriiminodiacetic acid). The X-ray crystal structure of {[Zn3(bmtac)(H2O)8] · 6H2O}2 reveals that all Zn(II) ions are six-coordinated with octahedral geometry. The dimer as basic building units assembled into a three-dimensional supramolecular framework through the multiple intermolecular O–H⋯O hydrogen bonds interactions. The complex shows a blue fluorescent emission band at 428 nm as the result of the intraligand (π–π) fluorescent emission.
Keywords: Hexanuclear zinc complex; Polycarboxylate; Dimer; Flexility;

Two novel tripodal ligands and their corresponding trinuclear Ru(II) complexes have been synthesized and characterized. These complexes exhibit abundant redox properties, show characteristic MLCT absorption band at 440 nm, and emitted at around 580 nm.Two polypyridyl ligands 2,2′,2″-tris((4,5-diazafluoren-9-yliminoxy)ethyl)amine (L1) and 1,3,5-tris((4,5-diazafluoren-9-yliminoxy)methyl))-2,4,6-trimethylbenzene (L2), and corresponding trinuclear Ru(II) complexes [(bpy)6L1−2(RuII)3](PF6)6 (Ru-L1, Ru-L2) have been synthesized. Cyclic voltammetry of the complexes are consistent with one Ru(II)-centered oxidation at 1.32 V and four ligand-centered reductions. Photophysical behaviors are investigated by UV–Vis absorption and fluorescence spectrometry. The two complexes show metal-to-ligand charge transfer absorption at 440 nm and emission at around 580 nm.
Keywords: Trinuclear Ru(II) complex; Electrochemistry; UV–Vis absorption; Emission;

Mononuclear and polynuclear complexes with a side-off compartmental Schiff base by F. Benetollo; P. Di Bernardo; S. Tamburini; P.A. Vigato; P. Zanonato (246-251).
d,f-Heteronuclear complexes with an acyclic Schiff bases with a ring contraction at one imine group takes place.The compartmental Schiff base H2-L, obtained by [2 + 1] condensation of 3-methoxy-2-hydroxybenzaldehyde and 1,5-diamino-3-azapentane, and the related mono- and hetero-polynuclear copper(II), zinc(II) and lanthanum(III) complexes have been prepared and their physico-chemical properties studied by IR, NMR, SEM-EDS and X-ray single crystal diffractometry. In the mononuclear complexes [M(L)] ·  nS (M = CuII, ZnII, S = H2O, MeOH), obtained in alcoholic solution by the reaction of the free ligand and the appropriate metal acetate hydrate or nitrate or by [2 + 1] condensation of the formyl- and polyamine-derivatives in the presence of the desired metal salt, [L]2− coordinates to the metal ion in the diimine form as ascertained by the 1H NMR spectra of the zinc(II) complex. The heterodinuclear complexes have been prepared by the reaction of the copper(II) or zinc(II) mononuclear complex with La(NO3)3  · 6H2O in 1:1 molar ratio. The copper–lanthanum complex is not a true heterodinuclear complex, as it can be described as {[Cu2(H2-L)2]2[La(NO3)6](NO3)}, while heterodinuclear complexation occurs in {[ZnLa(H-L′)(NO3)3(S)](NO3)} (S = H2O or C2H5OH), where a ring contraction at one imine group takes place, with the formation of a five-membered heterocyclic imidazolidine ring.
Keywords: Polynuclear complexes; Compartmental ligands; Schiff bases; Ring contraction; Imidazoline formation; Lanthanide complexes;

Cadmium(II) selenocyanate reacts with N,N′-dimethylimidazolidine-2-thione (Me2Imt) at a 1:1 ratio forming a polymeric [(Me2Imt)Cd(SeCN)2] complex.Cadmium(II) selenocyanate reacts with N,N′-dimethylimidazolidine-2-thione (Me2Imt) at a 1:1 ratio forming a polymeric [(Me2Imt)Cd(SeCN)2] complex. The metal ion is bonded to one imidazolidine thione through the sulfur atom, two selenocyanate ions through their selenium atoms and two other selenocyanates through their nitrogen atoms. The metal complex coordination sphere Cd[SSe2N2] adopts a distorted trigonal bipyramidal geometry with the chalcogen atoms occupying the equatorial positions and the nitrogen atoms in the axial positions. The 77Se CP MAS NMR data are consistent with two different selenium sites and the shielding tensor parameters of 113Cd point to a near axial symmetry for the cadmium environment.
Keywords: N,N′-Dimethylimidazolidine-2-thione; Cadmium selenocyanate; X-ray structure; 113Cd; 77Se CP MAS NMR;

Synthesis, structure and magnetic properties of one chiral heptanuclear Fe cluster: {Fe[(FeL)22-OH)]32-OH)6} · 13H2O by Xiao-Fang Ma; Jin-Lei Tian; Wen Gu; Song Gao; Shi-Ping Yan; Dai-Zheng Liao (256-259).
One new chiral heptanuclear FeIII cluster, {Fe[(FeL)22-OH)]32-OH)6} · 13H2O (1), has been synthesized and characterized structurally and magnetically. The heptanuclear FeIII cluster of 1 has a propeller-like [Fe72-OH)9]12+ core, with the peripheral ligation provided by six tetradentate L 2− ligands. Variable temperature magnetic studies showed 1 is antiferromagnetic with C = 14.27 cm3  K mol−1 and θ  = −27.56 K.One chiral heptanuclear FeIII cluster, {Fe[(FeL)22-OH)]32-OH)6} · 13H2O (1) (H2 L=N-(2-hydroxybenzyl)-l-histidine), has been synthesized and characterized structurally and magnetically. Complex 1 crystallizes in the chiral space group C2. The heptanuclear FeIII cluster of 1 has a propeller-like [Fe72-OH)9]12+ core, with the peripheral ligation provided by six tetradentate L 2− ligands. The configurations of the C- and the N-centers of L 2− is (S,  R) and the central atom Fe4 is chiral Λ configuration. All FeIII centers are hexacoordinated, displaying a distorted octahedral coordination sphere. Variable temperature magnetic studies showed complex 1 is antiferromagnetic with C  = 14.27 cm3  K mol−1 and θ  = −27.56 K. Magnetisation and susceptibility measurements show that cluster 1 exhibits a ground spin state of S  = 3.
Keywords: Heptanuclear; FeIII cluster; Crystal structure; Reduced Schiff base ligand; Chiral;

Three manganese coordination polymers [Mn(mbtz)2(dca)2(H2O)] n (1), [Mn(mbtz)2Cl2] n (2) and [Mn(mbtz)2(NCS)2] n (3) have been synthesized and characterized. There are two kinds of mbtz ligands in 1. One acts as bridging (bidentate) coordination mode. The other shows terminal (monodentate) coordination mode. The bridging mbtz ligands link the Mn(II) atoms to form the one-dimensional helical chain in 1, 2 and 3 are similar one-dimensional chain containing double bridges of mbtz ligand. 1, 2 and 3 all exhibit blue luminescent emissions maximum in the solid state at room temperature.One-dimensional chain manganese coordination polymers [Mn(mbtz)2(dca)2(H2O)] n (1), [Mn(mbtz)2Cl2] n (2) and [Mn(mbtz)2(NCS)2] n (3) (mbtz = 1,3-bis(1,2,4-triazol-1-ylmethyl)benzene, dca = dicyanamide) have been synthesized and characterized. X-ray crystal structure shows that there are two kinds of mbtz ligands in 1. One acts as the bridging (bidentate) coordination mode and shows the anti-conformation. The other shows the terminal (monodentate) coordination mode and exhibits the syn-conformation. The bridging mbtz ligands link the Mn(II) atoms to form the one-dimensional helical chain in 1, 2 and 3 are similar one-dimensional chain containing the double bridges of mbtz ligands. 1, 2 and 3 exhibit blue luminescent emissions maximum at 385, 405 and 414 nm, respectively, in the solid state at room temperature.
Keywords: One-dimensional chain; Helical; Coordination polymer; Manganese complex; Bis(1,2,4-triazol-1-ylmethyl)benzene; Luminescence;

A copper(II) complex with rare μ1,1,1-azide ligand: Active catalyst for heterogeneous olefin epoxidation by Partha Roy; Koushik Dhara; Mario Manassero; Pradyot Banerjee (265-269).
A copper(II) complex [Cu2 L1,1-N3)(μ1,3-N3)(μ1,1,1-N3)] where HL  = 4-methyl-2,6-bis(phenylmethyliminomethyl)phenol has been synthesized and characterized by X-ray crystallography. X-ray study reveals that it is a 1D chain and the existence of unusual μ1,1,1-azide bridging mode. The complex immobilized on mesoporous silica acts as an active catalyst for the epoxidation of olefins.A copper(II) complex [Cu2 L1,1-N3)(μ1,3-N3)(μ1,1,1-N3)] (1) where HL  = 4-methyl-2,6-bis(phenylmethyliminomethyl)phenol, with N2O donor ligand was synthesized and characterized by elemental analysis, FT-IR spectra and X-ray crystallography. X-ray crystallographic study reveals that it is a 1D chain along crystallographic b axis and the existence of rare μ1,1,1-azide bridging mode. The complex was immobilized on mesoporous silica and the immobilized compound was used as the active catalyst for the oxidation of olefins using tert-butyl hydroperoxide as oxidant. The results show that corresponding epoxides were produced in high yield with high selectivity.
Keywords: Cu(II) complex; Azide; Heterogeneous catalysis; Olefin epoxidation;

MoO2(acac)2 supported on silica functionalized imidazole as a highly efficient and reusable catalyst for alkene epoxidation with tert-BuOOH by Shahram Tangestaninejad; Majid Moghadam; Valiollah Mirkhani; Iraj Mohammadpoor-Baltork; Kamal Ghani (270-274).
The catalytic activity of molybdenyl acetylacetonate supported on silica functionalized imidazole, MoO2(acac)-SiIm, was investigated in the alkene epoxidation with tert-BuOOH. This heterogeneous catalyst can be applied for successful epoxidation of alkenes in refluxing 1,2-dichloroethane. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, UV–Vis spectroscopy, and SEM. This catalyst can be reused several times without significant of its catalytic activity.The catalytic activity of molybdenyl acetylacetonate supported on silica functionalized imidazole, MoO2(acac)-SiIm, was investigated in the alkene epoxidation with tert-BuOOH. This heterogeneous catalyst can be applied for successful epoxidation of alkenes in refluxing 1,2-dichloroethane. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, UV–Vis spectroscopy, and SEM. This catalyst can be reused several times without significant of its catalytic activity.
Keywords: Alkene epoxidation; Supported catalyst; TBHP; Molybdenyl acetylacetonate;

The synthesis of CNTs-B2O3 nanocomposite was accomplished based on the facile solvothermal reaction of (n-C4H9O)3B with carbon nanotubes in a Teflon coated stainless steel cylinder at 140 °C for 72 h. The X-ray powder diffraction pattern confirms boron oxide crystal phase in the composite.Single-walled carbon nanotube-B2O3 nanocomposite has been prepared using solvothermal technique. Tributyl borate was explored as the boron oxide reagent using toluene and water as the solvent, respectively. Characterization of the reaction products using Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction and thermogravimetric analysis confirmed the formation of the CNT-B2O3 nanocomposite. The solvothermal approach may serve as a facile strategy for synthesis of nanocomposites of metal oxides and carbon nanotubes especially when metal alkoxides is utilized as precursor for the metal oxides.
Keywords: Nanocomposite; Solvothermal; Tributyl borate; Boric oxide; Carbon nanotube;

Antiferromagnetic interactions in melamine-bridged trinuclear cobalt complex by Lei Zhang; Wei Li; Jian Zhang; Zhao-Ji Li; Ye-Yan Qin; Jian-Kai Cheng; Yuan-Gen Yao (279-282).
A new cobalt trimer complex, [Co3(ma)(ip)3] · 2H2O, has been synthesized hydrothermally and structurally characterized, which exhibits an interesting non-interpenetrated pseudo-pcu metal-organic 3D architecture constructed from a 6-connected SBU. The study of magnetic properties indicated that dominant antiferromagnetic coupling interactions exist between the adjacent Co(II) sites and between the adjacent trimers. And melamine molecule participates in transferring magnetic interactions for the first time.The hydrothermal assembly of Co(OAc)2  · 4H2O with isophthalatic acid (H2ip) and melamine (ma) yielded a novel 3D coordination polymeric complex, {[Co3(ma)(ip)3] · 2H2O} n (1), which presents an unusual non-interpenetrated pseudo-primitive cubic (pcu) topology constructed from a 6-connected trinuclear Co(II) SBU. The study of magnetic properties indicates that antiferromagnetic coupling interactions exist both between the adjacent Co(II) sites and between the adjacent trimers. So the melamine molecule participates in transferring magnetic interactions for the first time.
Keywords: Melamine; MOFs; Pcu; Antiferromagnetic coupling; Topology;

A novel germanium(IV) oxalate complex: [Ge(OH)2(C2O4)2]2− by Fa-Nian Shi; Luís Cunha-Silva; Filipe A. Almeida Paz; Michaele J. Hardie; Jacek Klinowski; João Rocha; Tito Trindade (283-287).
Two novel compounds, formulated as X ·  [Ge(OH)2(C2O4)2] ·  n(H2O) [where X = C 4 H 12 N 2 2 + (H2pipz2+) and n  = 1 for compound I, and X = C 10 H 10 N 2 2 + (H2bipy2+) and n  = 2 for II], were prepared from hydrothermal synthesis and characterised structurally using single-crystal X-ray diffraction, thermogravimetry, elemental analysis and vibrational spectroscopy (FT-IR and FT-Raman). The divalent anionic [Ge(OH)2(C2O4)2]2− complex is unprecedented.Two crystalline compounds, X · [Ge(OH)2(C2O4)2]·  n(H2O) [where X = C 4 H 12 N 2 2 + ( H 2 pipz 2 + ) and n  = 1 for compound I, and X = C 10 H 10 N 2 2 + ( H 2 bipy 2 + ) and n  = 2 for II], were synthesised using hydrothermal synthetic approach and characterised structurally using single-crystal X-ray diffraction, vibrational spectroscopy (FT-IR and FT-Raman), thermogravimetric analysis (TGA) and CHN elemental composition. The crystalline compounds contain a novel anionic complex [Ge(OH)2(C2O4)2]2−, which co-crystallises with organic cations (piperazinium in I, and 4,4′-bipyridinium in II) and water molecules of crystallisation. These chemical moieties are involved in extensive three-dimensional (3D) hydrogen bonding networks composed of strong and highly directional O–H⋯O and N–H⋯O interactions.
Keywords: Germanium(IV) oxalates; Hydrogen bonding networks; Crystalline structures; Crystalline organic-inorganic hybrids;

Structure and bonding in stretched σ-borane rhodium complexes [(η 5-C5H5)Rh(HBpin)2] 1Rh and [(η 5-C5H5)Rh(HBpin)(Bpin)2] 2Rh have been investigated. The optimized structure of 1Rh contains almost similar HBpin ligands. The B–H bond distances B1–H1, 1.696 Å and 1.747 Å in 1Rh and 1.686 Å in 2Rh are longer than expected for a single bond based on covalent radius predictions (1.19 Å) and those obtained by theoretical study for the free borane ligands (1.190 Å in HBpin). In 2Rh complex, less 2s character and more 2p character goes to the Rh–B2 and Rh–B3 bonds of boryl ligand than to the Rh–B1 bond of the borane ligand.A theoretical study of the stretched σ-borane complexes [(η 5-C5H5)Rh(HBpin)2] 1Rh and [(η 5-C5H5)Rh(HBpin)(Bpin)2] 2Rh (HBpin, pinacolborane) at the DFT BP86 levels has been carried out. In contrast to the previously optimized geometry of [(η 5-C5H5)Rh(HBO2C2H4)2], the optimized structure of 1Rh contains almost similar HBpin ligands. The B–H bond distances B1–H1, 1.696 Å and 1.747 Å in 1Rh and 1.686 Å in 2Rh are longer than expected for a single bond based on covalent radius predictions (1.19 Å) The B1–Rh–H1 bond angles 55.6° and 52.6° in 1Rh and 2Rh, respectively and B2–Rh–H2 bond angle in 1Rh are larger than the B–M–H bond angles in σ-borane complexes (37–41°) and are consistent with rhodium–σ-borane bonding, preserving some B–H bond character. The Rh–B and Rh–H bonding orbitals are strongly polarized towards rhodium.
Keywords: Rhodium; Borane complexes; Density functional calculations; Structure; Bonding;

Zinc(II) mediated cyclization and complexation of an unsymmetrical dicarboxyamine ligand, N-(2-carboxybenzomethyl)-β-alanine (H 2 cbal) have been studied in the solid state as well as in solution. The structural analyses reveal that while the cyclized ligand Hpda consists of an 1-oxo-1,3-dihydro-isoindol ring and is not coordinated to any zinc ion, the zinc complex 1 exhibits a three-dimensional coordination polymer constructed from mononuclear building unit, [NaZn(Hcbal)2(ClO4)] · H2O · CH3OH with the zinc center tetracoordinated in a distorted tetrahedral geometry. So, we have been able to isolate and characterise a new cyclized ligand and a new zinc coordination polymer using the reactions of same starting materials, the ligand H 2 cbal and Zn(ClO4)2  · 6 H2O, under two different reaction conditions.Zinc(II) mediated cyclization product, 3-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (Hpda) and complexation of the unsymmetrical amino dicarboxylic ligand, N-(2-carboxybenzomethyl)-β-alanine (H 2 cbal), have been isolated and their crystal structures determined.
Keywords: Reduced Schiff base; Cyclization; Zinc complex; Coordination polymer; Crystal structures; NMR;

A gold electrode was modified with mercaptoacetate to serve to anchor Ru(III) and the interactions of this self-assembled complex with hexacyanoferrate, ethylenediamminetetraacetate and nitric oxide was studied.A gold electrode was modified with mercaptoacetate to serve to anchor Ru(III) and the interactions of this self-assembled complex with hexacyanoferrate, ethylenediamminetetraacetate and nitric oxide was studied.
Keywords: Mercaptoacetate; Ruthenium(III) complex; Self-assembly; Nitric oxide; Hexacyanoferrate; Ethylenediamminetetraacetate;

The first nickel(II) complex with a 2-aminoglucose Schiff-base ligand representing a monomeric chitosan model with trans-configured 2,3-chelation by the sugar backbone is reported. The complex shows extensive hydrogen bonding and π-stacking in the crystal lattice. The distorted octahedral geometry at the nickel(II) ions leads to a rather large zero-field-splitting.Based on the sugar-modified Schiff-base ligand derived from salicylaldehyde and benzyl 2-deoxy-2-amino-α-d-glucopyranoside (H2salagluc) the new mixed-ligand nickel(II) complex [Ni(Hsalagluc)(tptz)]ClO4 has been synthesized (tptz = 2,4,6-tri-(2-pyridyl)-1,3,5-triazine). The X-ray crystal structure reveals a distorted octahedral geometry at the nickel(II) center with the rare 2,3-chelation of the trans-configured donor atoms of the carbohydrate backbone. Intermolecular hydrogen bonding leads to dimeric units of the complex cations. The supramolecular assembly of these units by π-stacking of the tptz coligands affords one-dimensional chains along the two fold screw axis. O–H⋯π(Ar) hydrogen bonding is observed for a methanol molecule of crystallization. Magnetic susceptibility measurements are consistent with a high-spin nickel(II) ion with a zero-field-splitting of D  = −11.5 cm−1 (g  = 2.311).
Keywords: Carbohydrates; Schiff-bases; Nickel(II) complexes; Supramolecular chemistry; Self-assembly; π-Stacking;

Two dibenzo-O2S2 macrocycles L 1 and L 2 were employed as soft donor ligands towards Pd(II). Two-step approach via reaction of 1:1-type complex, [cis-Cl2(L 1)Pd], with L 2 through a successive treatment of AgClO4 has led to the isolation of a co-crystallised bis(O2S2 macrocycle) Pd(II) complex 1, {[Pd(L 1)2] · [Pd(L 2)2]}(ClO4)4 containing two different homo-ligand bis(O2S2 macrocycle) analogues. In solution, formation of the mixed-ligand bis(O2S2 macrocycle) complex [Pd(L 1)(L 2)]2+ was confirmed.Two dibenzo-O2S2 macrocycles (L 1: 15-membered, L 2: 14-membered analogue) were employed as soft donor ligands towards palladium(II). Two-step approach via reaction of 1:1-type complex, [cis-Cl2(L 1)Pd], with L 2 through a successive treatment of AgClO4 has led to the isolation of a co-crystallised bis(O2S2 macrocycle) palladium(II) complex 1, {[Pd(L 1)2] · [Pd(L 2)2]}(ClO4)4 containing two different homo-ligand bis(O2S2 macrocycle) analogues. In solution, on the other hand, formation of the mixed-ligand bis(O2S2 macrocycle) complex [Pd(L 1)(L 2)]2+ was also confirmed by electro-spray ionisation mass spectrometry.
Keywords: Bis(O2S2 macrocycle) palladium(II) complex; Co-crystallisation; Crystal structure; ESI-mass;

Novel ruthenium complexes containing monodentate- or bidentate azopyridyl ligands are prepared. The complexes exhibit different azo ligand-based two-electron reduction behavior depending upon the coordination modes of the azopyridyl ligand.Novel ruthenium carbonyl complexes containing an azopyridyl ligand were prepared and their molecular structures determined by X-ray crystallography. The complexes exhibited different azo ligand-based two-electron reduction behavior in electrochemical measurements, depending on the coordination modes of the azopyridyl ligand.
Keywords: Ruthenium; Azopyridyl ligand; Electrochemistry; Crystal structures; Carbonyl complexes;

A novel water aggregate, comprised of alternate octameric water cubes and (H2O)20-cluster units, encapsulated within 3d–4f metal–organic networks [{Ln2M3(3,5-pdc)6(H2O)22} · 20.5H2O] n (Ln = Sm, Eu, Gd; M = Co, Ni) is presented.A novel water aggregate, comprised of alternate octameric water cubes and (H2O)20-cluster units, encapsulated within 3d–4f metal–organic networks [{Ln2M3(3,5-pdc)6(H2O)22} · 20.5H2O] n (Ln = Sm, Eu, Gd; M = Co, Ni) is presented.
Keywords: Water cluster; Water cube; Water aggregate; Metal–organic networks;

Anion recognition by a novel zinc(Π) xanthone–crown ether complex by Rui Shen; Xiaobo Pan; Huifang Wang; Jincai Wu; Ning Tang (318-322).
A novel zinc(Π) xanthone–crown ether complex was synthesized and studied as anion–receptor. The results show the Zn (Π) xanthone–crown ether complex is a sensitive and selective fluorescent chemosensor for HSO 4 - .A novel Zn(Π) xanthone–crown ether complex (2) was synthesized and demonstrated to selectively detect HSO 4 - over other anions by fluorescence and UV–vis absorption spectroscopy. In contrast, xanthone–crown ether (1) did not show detectable affinity for all the anions examined.
Keywords: Zn(Π) xanthone–crown ether complex; Anion recognition; Fluorescent chemosensor;

Extraordinary dissolution of coordination polymer, La[Fe(CN)6] · 5H2O, in ethylene glycol/water mixed solvent and structural determination of dissolved species by Aya Nakajima; Shun Itoh; Masato Kurihara; Masatomi Sakamoto; Daisuke Yoshioka; Masahiro Mikuriya; Satoshi Hamakawa; Fujio Mizukami (323-325).
Heteronuclear coordination polymer, La[Fe(CN)6] · 5H2O, poorly soluble in water and almost insoluble in usual organic solvents was found to be tremendously dissolved in a mixed solvent of ethylene glycol (EG):water = 7:3 to give a highly viscous solution which is a promising fluid precursor for the wide application of La[Fe(CN)6] · 5H2O to functional materials. Structure of single crystals isolated from this solution was determined to elucidate the high solubility.Heteronuclear coordination polymer, La[Fe(CN)6] · 5H2O, poorly soluble in water and almost insoluble in usual organic solvents due to its sturdy three-dimensional infinite network structure constructed by Fe–CN–La linkages was found to be tremendously dissolved in the mixed solvent of ethylene glycol (EG):water = 7:3 to give a highly viscous solution as a promising fluid precursor for the wide application of La[Fe(CN)6] · 5H2O which has been so far utilized only as a solid precursor of LaFeO3. Structure of single crystals isolated from this viscous solution was determined to elucidate the high solubility of La[Fe(CN)6] · 5H2O.
Keywords: Lanthanum(III) hexacyanoferrate(III); Solubility; Ethylene glycol complex of lanthanum(III); Crystal structure;

This work describes the hydrothermal synthesis, characterization, and thermal stability of a CdII coordination polymer, which displays a unique bilayer coordination framework with mixed-connected network topology.A unique CdII coordination polymer {[Cd2(pyt)2(chdc)(H2O)](H2O)2} n (1) has been obtained by hydrothermal reaction and characterized by IR, microanalysis, and powder X-ray diffraction (here Hpyt = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol and H2chdc = 1,4-cyclohexanedicarboxylic acid). Single crystal X-ray diffraction reveals that complex 1 has an unusual bilayer coordination framework with mixed-connected network topology, in which two adjacent [Cd(pyt)] n layers are spaced by chdc pillars. Thermal stability of 1 has also been discussed.
Keywords: Hydrothermal synthesis; Crystal structure; Coordination polymer; Bilayer framework; Network topology;

Intramolecular hydrogen bond controlled monodentate S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II) by Damir A. Safin; Łukasz Szyrwiel; Sergey V. Baranov; Felix D. Sokolov; Maria G. Babashkina; Henryk Kozlowski (330-333).
We reported three new complexes of the Pd(II) cation with N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)2 (R =  tBu, HL I; R = Ph, HL II; R = 4′-benzo-15-crown-5, HL III). Structures of the obtained compounds were investigated by IR, 1H and 31P{1H} NMR spectroscopy and elemental analysis. The crystal structure of complex trans-Pd(HLI-S)2Cl2 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C=S groups and the chlorine atoms. Complexes trans-Pd(HLI–III-S)2Cl2 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only.Reaction of N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)2 (R =  tBu, HL I; R = Ph, HL II; R = 4′-benzo-15-crown-5, HL III) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of formulae Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C=S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only.
Keywords: Complex; Crown-ether; Monodentate coordination; Palladium(II); Thiourea;

A new copper-complex fragment-substituted β-octamolybdate, K2[{Cu(phen)}4Mo6O22][Mo8O26] · 2H3O (1) (phen = 1,10-phenanthroline), has been hydrothermally synthesized and structurally characterized. The compound 1 is first observation of one-dimensional linear chain structure containing transition-metal-substituted dilacunary β-octamolybdate fragments [{Cu(phen)}4Mo6O22] and [β-Mo8O26]4− clusters.A copper-complex fragments-substituted β-octamolybdate, K2[{Cu(phen)}4Mo6O22][Mo8O26] · 2H3O (1) (phen = 1,10-phenanthroline), has been hydrothermally synthesized and structurally characterized for the first time. Compound 1 is constructed from transition-metal-substituted dilacunary β-octamolybdate fragment [{Cu(phen)}4Mo6O22] and [β-Mo8O26]4− cluster to form one-dimensional (1D) linear chain. Furthermore, magnetic measurements show weak ferromagnetic interactions for compound 1.
Keywords: Polyoxometalates; Copper-complex fragments-substituted; Dilacunary β-octamolybdate; Magnetic property;

Synthesis and characterization of phosphonic acid-substituted porphyrazines by Nürüfe Kemikli; Ramazan Öztürk (338-340).
The novel peripherally phosphonate-substituted porphyrazine was synthesized from 1,2-bis{2-(diethyl phosphonate) ethylthio}maleonitrile and phosphonate units were converted to phosphonic acid by TMSBr.Porphyrazines with phosphonic acid groups on the peripheral positions have been prepared by the cyclotetramerization of 1,2-bis{2-(diethyl phosphonate)ethylthio} maleonitrile and followed by the cleavage of the phosphonate esters with TMSBr.
Keywords: Porphyrazine; Phosphonic acid; Supramolecule; TMSBr;

A cyano-bridged Mn 2 III Cr III complex: Synthesis, structure and magnetic properties by Yuhua Feng; Chao Wang; Gongfeng Xu; Yan Ouyang; Daizheng Liao; Shiping Yan (341-344).
A novel cyano-bridged Mn 2 III Cr III complex {Cr(CN)4[CNMn(salen)(MeOH)]2} {[Mn(salen)(CH3OH)(H2O)]2}[Mn(salen)(MeOH)]2[Cr(CN)6] · 6CH3OH (1) (salen =  N,N′-ethylene-bis-salicylideneaminato) has been synthesized and characterized. X-ray structure analysis reveals that in 1, except for the trinuclear Mn 2 III Cr III unit, there exist two mononuclear and one dimeric MnIII Schiff-base units.A novel cyano-bridged Mn 2 III Cr III complex {Cr(CN)4[CNMn(salen)(MeOH)]2}{[Mn(salen)(CH3OH)(H2O)]2}[Mn(salen)(MeOH)]2[Cr(CN)6] · 6CH3OH (1) (salen =  N,N′-ethylene-bis-salicylideneaminato) has been synthesized and structurally characterized. X-ray structure analysis reveals that in 1, except for the trinuclear Mn 2 III Cr III unit, there exist two mononuclear MnIII and one dimeric MnIII Schiff-base units. All these structural units are linked by hydrogen bond into a 3D network. The magnetic characterization shows that compound 1 displays a weak ferromagnetic behavior.
Keywords: Cyano-bridged complex; Manganese(III) Schiff-base; Hydrogen bond; Magnetic property;

Four tetranuclear complexes {[Ln2(2-SB)3(phen)3(H2O)2] ·  nH2O}2 (Ln = Sm (1), n  = 3; Ln = Eu (2), n  = 2; Ln = Tb (3), n  = 2; and Ln = Dy (4), n  = 2.5; 2-SB = 2-sulfobenzoate, phen = 1,10-phenanthroline) were formed by 2-sulfobenzoate linker. It is first example of tetranuclear lanthanide complex of metal centers through carboxylate group linker.Four novel complexes {[Ln2(2-SB)3(phen)3(H2O)2] ·  nH2O}2 (Ln = Sm (1), n  = 3; Ln = Eu (2), n  = 2; Ln = Tb (3), n  = 2; and Ln = Dy (4), n  = 2.5; 2-SB = 2-sulfobenzoate, phen = 1,10-phenanthroline), were synthesized by hydrothermal reactions and characterized using single-crystal X-ray diffraction, thermogravimetric analyses and luminescence spectroscopy. In the four complexes, there are two types of Ln(III) ion coordination environments. Ln(III) ions are connected together through 2-SB ligands via μ2-, η3- and η2-coordination modes, resulting in a tetranuclear molecule with central symmetry, indicating novel structural features. The emission spectra of the four complexes indicate the typical luminescence characteristics of the Sm(III) for 1, Eu(III) for 2, Tb(III) for 3, and Dy(III) ions for 4, respectively.
Keywords: Lanthanide complex; Tetranucleus; 2-Sulfobenzoate; Hydrothermal synthesis; Crystal structure; Luminescence;

Reduction of samarium Schiff base chloride L2SmCl(THF) (1) ( L = 3 , 5 - Bu 2 t - 2 -O – C 6 H 2 CH – N – 8 - C 9 H 6 N ) with excessive metallic sodium produced an unprecedented samarium complex [ Na ( DME ) 3 ] [ SmL 3 ′ Na ( DME ) ] (2), in which three Schiff base ligands were trimerized to form the new ligand L 3 ′ by the reductive coupling reactions of imine groups involving a rare coupling reaction of C=N bond of quinoline ring with imine group of Schiff base ligand.SmCl3 reacted with sodium salt of the Schiff base ligand L ( L = 3 , 5 - Bu 2 t - 2 -O – C 6 H 2 CH – N- 8 - C 9 H 6 N ) in a 1:2 molar ratio in THF to afford samarium Schiff base chloride L2SmCl(THF) (1). Treatment of complex 1 with excessive metallic sodium produced an unprecedented samarium complex [ Na ( DME ) 3 ] [ SmL 3 ′ Na ( DME ) ] (2), in which three Schiff base ligands were trimerized to form the new ligand L 3 ′ by the reductive coupling reactions of imine groups involving a rare coupling reaction of C=N bond of quinoline ring with imine group of Schiff base ligand.
Keywords: Schiff base ligand; Samarium complex; Reductive coupling; Synthesis;