Inorganic Chemistry Communications (v.11, #9)

Contents List (iii-xv).

A novel microporous compound [Co22-OH2)2(H2O)8][H2(TC-TTF)]2  · 2H2O was self-assembled from the ligand H4(TC-TTF). The compound forms a 3D supramolecular network through hydrogen-bonding and S···S interactions and shows an 1D microporous open channel (3.5 × 4.7 Å). Variable-temperature magnetic susceptibility measurement at 1.8–300 K reveals weak ferromagnetic coupling between CoII ions.A novel microporous complex [Co22-OH2)2(H2O)8][H2(TC-TTF)]2  · 2H2O [H4(TC-TTF) = tetra(carboxyl)tetrathiafulvalene] was self-assembled from H4(TC-TTF) and CoCl2  · 6H2O. The complex forms a 3D supramolecular network through hydrogen-bonding and S···S interactions and shows an 1D microporous open channel along the a axis (3.5 × 4.7 Å). Variable-temperature magnetic susceptibility measurement at 1.8–300 K reveals weak ferromagnetic coupling between CoII ions.
Keywords: Cobalt (II) complex; Magnetic properties; Hydrogen bonds; H4(TC-TTF);

One-dimensional (1D) helical and 2D homochiral metal–organic frameworks built from a new chiral octahydrobinaphthalene-derived dicarboxylic acid by Xiang Ouyang; Zhenxia Chen; Xiaofeng Liu; Yongtai Yang; Mingli Deng; Linhong Weng; Yaming Zhou; Yu Jia (948-950).
Three homochiral metal–organic frameworks are obtained using enantiopure octahydrobinaphthyl-derived dicarboxylic acid as bridging ligands and transition metal ions. Two polymeric motifs were observed in these compounds: the one-dimensional infinite chiral helical structure and the two-dimensional rhombic grids network.Three homochiral metal–organic frameworks (MOFs) based on enantiopure chiral ligand: (R)-2,2’-dimethoxy-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-3,3′-dicarboxylic acid (H2L), namely Cd(L)(Py)3 1, Cu(L)(Py)3 2, Na[Cd(L)(LH)] · 2.5H2O 3 (Py = pyridine), were firstly synthesized, under solvothermal reactions. X-ray single-crystal diffraction studies reveal that 1 and 2 adopt one-dimensional (1D) infinite helical structures, while 3 possesses 2D chiral framework structure adopting ABAB offset stacking modes along the a-axis. Thermogravimetric analyses (TGA) display that 3 is thermally stable to 330 °C which is rare for homochiral MOFs.
Keywords: Chiral ligand; Helical; Homochiral metal–organic frameworks; Solvothermal reaction;

A novel 3D microporous metal-organic framework of cadmium(II) oxalate with diamondoid network by Rui-Qin Zhong; Ru-Qiang Zou; Daya S. Pandey; Tetsu Kiyobayashi; Qiang Xu (951-953).
Three-dimensional metal-organic framework of cadmium(II) oxalate with diamondoid topology and open channels was created by decomposition of pyridine-2,4,6-tricarboxylic acid under solvothermal reaction, exhibiting high thermostability and nitrogen adsorption capability.A three-dimensional (3D) metal-organic framework of cadmium(II) oxalate, [Cd(C2O4)2(H2O)](H2O)(H3O)2(C2H5OH) 1, has been created by decomposition of pyridine-2,4,6-tricarboxylic acid under solvothermal reaction condition. Single crystal X-ray diffraction analysis shows that complex 1 self-assembles into a 3D noninterpenetrated diamondoid network with open channels accommodating guest ethanol and water molecules. The thermostability and nitrogen adsorptive property of 1 were investigated.
Keywords: Solvothermal synthesis; Oxalate; Diamondoid network; Thermostability; Adsorptive property;

Two copper coordination polymers were assembled by polycarboxylates and 2,6-bis(1,2,4-triazolyl)pyridine. One is a ferromagnetic CuII complex, the other one is a CuI/CuII mixed-valence complex.Hydrothermal reactions of Cu(NO3)2 with 2,6-bis(1,2,4-triazolyl)pyridine (btp) and 1,3,5-benzenetricarboxylic acid (H3btc) or 1,2,4,5-benzenetetracarboxylic acid (H4btec) in base aqueous solution afford two novel complexes [Cu2(btp)(btc)(H2O)(OH)] n (1) and [Cu2(btp)(Hbtec)] n  ·  nH2O (2). Complex 1 is a coordination polymer where a carboxylate and a hydroxyl are bound to Cu(II) ions to form (μ-OH)(μ-O2CR)Cu2 core, which is ferromagnetic couple with 2 J = 21.30 cm−1. Complex 2 is a 3-D coordination polymer. Bond valence sum (BVS) analysis indicates it is a mixed-valence compound. Cu(I) is three-coordinated by triazole N-donors, while Cu(II) is four-coordinated by a triazole N and three carboxyl O-donors. Both complexes are quite thermal stable.
Keywords: Copper complex; Crystal structure; 2,6-Bis(1,2,4-triazolyl)pyridine; 1,3,5-Benzenetricarboxylic acid; 1,2,4,5-Benzenetetracarboxylic acid; Mixed-valence; Magnetism;

A novel 4 · 82 CdII network constructed from helical motif: Incorporating alternate left- and right-hand helical water chains by Meili Zhang; Dongsheng Li; Feng Fu; Xiaogang Yang; Yapan Wu; Enbo Wang (958-960).
A novel 2D 4 · 82 CdII network with alternating heterochiral motif was reported, which is extended to 3D through π–π stacking. Interestingly, 1D hydrophilic tunnel of 3D architecture, providing potential helical hydrogen-bonded identification sites, acts as a template for the formation of the alternate left- and right-handed 1D helical water chains. The compound exhibits intense photoluminescence at room temperature.A novel 2D 4 · 82 CdII network with alternating heterochiral motif was reported, which is extended to 3D through π–π stacking. Interestingly, 1D hydrophilic tunnel of 3D architecture, providing potential helical hydrogen-bonded identification sites, acts as a template for the formation of the alternate left- and right-handed 1D helical water chains. The compound exhibits intense photoluminescence at room temperature.
Keywords: CdII network; Crystal structure; Helix; Water chain; Luminescence;

A Cu(II)-catalyzed oxidative substitution of pyrazole-3,5-dicarboxylic acid (H3pdc) C–H bonds by bromo/iodo nucleophiles in a self-assembly process under hydrothermal conditions afforded the first halogenated pyrazolecarboxylato-based linear trinuclear copper(II) coordination complexes.A Cu(II)-catalyzed oxidative substitution of pyrazole-3,5-dicarboxylic acid (H3pdc) C–H bonds by bromo/iodo nucleophiles in a self-assembly process under hydrothermal conditions afforded the first halogenated pyrazolecarboxylato-based linear trinuclear copper(II) coordination complexes.
Keywords: C–H activation; Pyrazole-3,5-dicarboxylate; Cu(II) complex; Halogenated;

A new 2D layered framework, [Mn(L)2(OAc)2] n  ·  nH2O (L = 3-amino-1H-1,2,4-triazole), was hydrothermally synthesized with structure and fluorescence characterized. Two kinds of edge-sharing 16-membered rings are formed by four L ligand alternately connecting four Mn(II) centers, whose fuse produces a wave-like 2D layer and further fabricated into a supramolecular architecture through the hydrogen bondings.A new 2D layered compound, [Mn(L)2(OAc)2] n  ·  nH2O (L = 3-amino-1H-1,2,4-triazole), was hydrothermally synthesized with structure and fluorescence characterized. Four L ligands alternately connect four Mn(II) centers into two kinds of edge-sharing 16-membered rings, whose fuse produces a wave-like 2D layer. The 2D layers are further fabricated into a supramolecular architecture through the hydrogen bondings. With the similar fluorescent features of free L ligand, the title compound produced pale blue fluorescence at 419 nm, which is assigned to π···π intra ligand transition of triazole ring.
Keywords: Crystal structure; Fluorescence; Manganese; 1,2,4-triazole;

A 3D-diamond-like tetrazole-based Zn(II) coordination polymer: Crystal structure, nonlinear optical effect and luminescent property by Qi-Yong Chen; Yan Li; Fa-Kun Zheng; Wen-Qiang Zou; Mei-Feng Wu; Guo-Cong Guo; A-Qing Wu; Jin-Shun Huang (969-971).
A terazole-based Zn(II) coordination polymer with a 3D-diamond-like net has been synthesized and structurally characterized, which exhibits a second-order nonlinear optical effect comparable to KDP and displays strong blue emission originating from intraligand charge transition.A tetrazole-based Zn(II) coordination polymer, [Zn(tzf)2]n 1 (Htzf = 1H-tetrazole-5-formic acid), was synthesized by reaction of ZnCl2 and Htzf, and structurally characterized by single-crystal X-ray diffraction. Polymer 1 features a 3D-diamond-like net formed by the linkage of Zn(II) atoms and tetrazole groups. The carboxylate O atoms in tzf ligand remain uncoordinated. Polymer 1 displays a second harmonic generation response, which is ca. 1.1 times that of KDP (KH2PO4). The photoluminescent analysis reveals that 1 exhibits strong blue emission resulting from intraligand charge transition.
Keywords: Coordination polymer; 1H-Tetrazole-5-formic acid; Crystal structure; Diamond-like network;

The influence of the substituents at N1 nitrogen on geometry of nickel(II) complexes with heterocyclic thiosemicarbazones by Tarlok S. Lobana; Poonam Kumari; Matthias Zeller; Ray J. Butcher (972-974).
The influence of the substituents at N1 nitrogen on geometry of nickel(II) complexes with heterocyclic thiosemicarbazones is investigated. Furan-2-carbaldehyde-N-phenyl-thiosemicarbazone has formed a cis-square planar complex 3 and thiophene-2-carbaldehyde-N-phenyl-thiosemicarbazone has yielded a trans square planar complex 6.The influence of the substituents (R) at the N1 nitrogen of heterocyclic thiosemicarbazones {(C4H3X)–C(H)=N3–N2H–C1(=S)N1HR; X = O, Hftsc; S, Httsc} on the geometry of nickel(II) complexes was investigated. Furan-2-carbaldehyde thiosemicarbazones have formed both trans [Ni(ftsc-N-R)2] (R = Me, 1; Et, 2), and cis (R = Ph, 3), square planar complexes unlike thiophene-2-carbaldehyde thiosemicarbazones which yielded only trans square planar complexes [Ni(ttsc-N-R)2] (R = Me, 4; Et, 5; Ph, 6).
Keywords: Furan-2-carbaldehyde-N-methyl thiosemicarbazone; Thiophene-2-carbaldehyde-N-phenyl thiosemicarbazone; Nickel; Square planar complex;

A protected ethynyl group was introduced into a γ-position of a (β-diketonato)bis(bipyridine)ruthenium(II) complex through the reaction of the bromo complex and (triisopropylsilyl)-acetylene with very good yield under microwave irradiation. Two new mononuclear mixed-ligand ruthenium(II) complexes, [Ru(bpd)(bpy)2](PF6) (2; bpy = 2,2′-bipyridine, bpd = 3-bromo-2,4-pentanedionate ion) and [Ru(tipsepd)(bpy)2](PF6) (3; tipsepd = 3-((triisopropylsilyl)ethynil)-2,4-pentanedionate ion) were then prepared.A protected ethynyl group was introduced into a γ-position of a (β-diketonato)bis(bipyridine)ruthenium(II) complex through the reaction of the bromo complex and (triisopropylsilyl)-acetylene with very good yield under microwave irradiation. Two new mononuclear mixed-ligand ruthenium(II) complexes with bipyridine (bpy) and functionalized acetylacetonate ion (2,4-pentanedionate, acac), [Ru(bpd)(bpy)2](PF6) (2; bpy = 2,2′-bipyridine, bpd = 3-Bromo-2,4-pentanedionate ion) and [Ru(tipsepd)(bpy)2](PF6) (3; tipsepd = 3-((triisopropylsilyl)ethynil)-2,4-pentanedionate ion) were then prepared as candidates for building blocks. The 1H NMR, UV–Vis, electrochemistry and FAB mass spectral data of these complexes are presented. X-Ray single crystal diffraction analysis has been made on complex 2, it crystallized with empirical formula of C25H22BrF6N4O2PRu, in a monoclinic crystal system and space group C2/c with a  = 29.340(5) Å, b  = 13.282(2) Å, c  = 15.7492 (14) Å, β  = 109.452(8)°, V  = 5786.9(13) Å3 and Z  = 8.
Keywords: Ruthenium(II) bipyridyl complex; β-diketone complex; Acetylenic compounds; Mixed-ligand; X-Ray structure; Microwave irradiation synthesis;

A 3D 3d–4f coordination polymer, {[Cu10Er4(IN)14ClBr7(H2O)10] · 2H2O} n (1) [IN = isonicotinic acid], has been hydrothermal synthesized and characterized. Complex 1 shows a rare 3D heterometallic coordination framework. Furthermore, the luminescent properties of complex 1 have also been investigated.A 3d–4f heterometallic coordination polymer, {[Cu10Er4(IN)14ClBr7(H2O)10] · 2H2O} n (1) [IN = isonicotinate], has been synthesized by hydrothermal reaction of the ligand with CuBr2, NaCl and Er2O3. Complex 1 represents a rare 3D heterometallic coordination framework constructed from Er-carboxylate subunits and unique Cu-halide (Br/Cl) chains that are bridged by a single type of linear ligand. Furthermore, the luminescent properties of complex 1 have also been investigated.
Keywords: Hydrothermal synthesis; Heterometallic complex; Isonicotinic ligand; Cu-halide chains;

Novel cationic copper coordination frameworks constructed from copper phosphate 8-rings and 4,4′-bisimidazolylbiphenyl as a bridging ligand by Liangming Hu; Elinor C. Spencer; Guangbin Wang; Gordon Yee; Carla Slebodnick; Brian E. Hanson (982-984).
In this article we report on the preparation and structural and mangnetic analysis of two novel copper(II) networks comprising unique cationic copper–phosphate 8-rings that are linked by the rigid difunctional ligand 4,4′-bisimidazolylbiphenyl to form one-dimensional and three-dimensional cationic hybrid networks.Two cationic hybrid networks, the first one-dimensional and the second three-dimensional, comprising unique cationic copper–phosphate 8-rings that are linked by the rigid difunctional ligand 4,4′-bisimidazolylbiphenyl are reported. These complexes have been characterized fully by single-crystal X-ray diffraction and magnetic studies.
Keywords: Magnetic studies; Copper complex; Metal–organic framework; Bisimidazolylbiphenyl; Tetranuclear ring;

Synthesis and structure study of a novel 2D network polymeric cadmium(II) complex bridged by thiocyanate by Chang Gao; Yongzhong Wu; Haibo Gong; Xiaopeng Hao; Xiangang Xu; Minhua Jiang (985-987).
A distorted honeycomb-like cadmium-thiocyanate framework with the formular [BMIM]2[Cd2(SCN)6] has been synthesized by self-assembling through electrostatic interaction between cadmium–thiocyanate network and N,N′-dialkylimidazolium ions. The [BMIM]+ cations acting as the spacers and controllers dominate the dimension of the complex.A distorted honeycomb-like cadmium–thiocyanate framework with the formular [BMIM]2[Cd2(SCN)6] has been synthesized by self-assembling through electrostatic interaction between cadmium–thiocyanate network and N,N′-dialkylimidazolium ions. The [BMIM]+ cations acting as the spacers and controllers dominate the dimension of the complex.
Keywords: 2D network; Cadmium–thiocyanate; Alkylimidazol; Sandwich complex;

Synthesis and structure of the first clathrochelate ligand with a cis-diimidazolyl donor fragment by Yan Z. Voloshin; Oleg A. Varzatskii; Zoya A. Starikova; Alexander S. Belov; Anatoly V. Ignatenko; Yurii N. Bubnov (988-991).
The monoribbed-functionalized clathrochelate with two functionalizing imidazolyl substituents was synthesized by interaction of dichloroglyoximato-bis-α-benzyldioximate FeBd2(Cl2Gm)(BF)2 precursor with organomagnesium imidazole derivative. The N6 -coordination polyhedron of the diimidazolyl iron(II) clathrochelate molecule has a distorted trigonal prismatic geometry with the distortion angle φ  = 24.1° and the Fe―N distances approximately 1.91 Å.The monoribbed-functionalized clathrochelate with two functionalizing imidazolyl substituents was synthesized by interaction of dichloroglyoximato-bis-α-benzyldioximate FeBd2(Cl2Gm)(BF)2 precursor with organomagnesium imidazole derivative. The N6 -coordination polyhedron of the diimidazolyl iron(II) clathrochelate molecule has a distorted trigonal prismatic geometry with the distortion angle φ  = 24.1° and the Fe―N distances approximately 1.91 Å.

Zn(2,2′-bipy)2/Co(2,2′-bipy)2 linked decaniobate [Nb10O28]6− clusters–zigzag neutral chains by Long Shen; Chun-Hong Li; Ying-Nan Chi; Chang-Wen Hu (992-994).
The decaniobate [Nb10O28]6–-linked by Zn(2,2′-bipy)2 or Co(2,2′-bipy)2 is first observed in polyoxoniobate chemistry as the first examples of decaniobate polymers.Two isostructural decaniobate polymers {[Zn(2,2′-bipy)2]3[Nb10O28] · 3H2O} n (1) and {[Co(2,2′-bipy)2]3[Nb10O28] · 1.5H2O} n (2) have been assembled successfully based on [M(2,2′-bipy)2] (M = Zn and Co) and metastable [Nb10O28]6− clusters under mild hydrothermal condition. The two compounds have been characterized by IR, TG analysis and single-crystal X-ray diffraction. The decaniobate [Nb10O28]6− linked by Zn(2,2′-bipy)2 or Co(2,2′-bipy)2 is first observed in polyoxoniobate chemistry as the first examples of decaniobate polymers.
Keywords: Decaniobate; Hydrothermal condition; Zinc; Cobalt; 2,2′-Bipyridine;

Delving into the second supramolecular event approach: Aggregation of small metallo-supramolecular units supported by one or two types of non-covalent forces by Miguel Vázquez López; Guillermo Zaragoza; Rosa Pedrido; Gustavo Rama; Manuel R. Bermejo (995-998).
The neutral single-stranded monohelicate [Pd(HL)]·2(CH3CN) (1) aggregates in the solid state to give an infinite 1D supramolecular chain through either the cooperative action of hydrogen bonding and π-stacking interactions or by aromatic π-stacking alone.The neutral single-stranded monohelicate [Pd(HL)]·2(CH3CN) (1) aggregates in the solid state to give an infinite 1D supramolecular chain through either the cooperative action of hydrogen bonding and π-stacking interactions or by aromatic π-stacking alone.
Keywords: Helicate; Palladium(II); Hydrogen bond; π-Stacking; Supramolecular chemistry;

Recognition of phosphate anions in aqueous solution by a dinuclear zinc(II) complex of a cyclen-tethered terpyridine ligand by Jun Du; Xiaoyong Wang; Mo Jia; Tuanjie Li; Jiafei Mao; Zijian Guo (999-1002).
A dizinc complex of 1-[4′-p-tolyl-(2,2′:6′,2″-terpyridyl)]-1,4,7,10-tetraazacyclododecane demonstrates a selective recognizing ability for phosphate anions, which can be sensed by fluorescence and UV spectroscopy in aqueous solution.A dizinc complex of 1-[4′-p-tolyl-(2,2′:6′,2″-terpyridyl)]-1,4,7,10-tetraazacyclododecane selectively recognizes phosphate anions in aqueous solution and the recognition process can be sensed by remarkable changes in fluorescence and UV spectroscopy.
Keywords: Anion; Receptor; Luminescence; N ligand; Zinc;

The preparation and the r.t. luminescence of the complexes [Cu(binap)2]+ and [Cu(binap)I]2 with binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl are reported. The lowest-energy excited state of [Cu(binap)2]+ is an IL ππ state of the binaphthyl chromophore. The luminescence of the cation consists of a fluorescence and a phosphorescence originating from this IL state. In contrast, the dimer [Cu(binap)I]2 is characterized by a I  → binap LLCT state which occurs at lower energies than the binap IL state. The dimer shows only a single emission band. This luminescence is suggested to come from the LLCT triplet.The preparation and the r.t. luminescence of the complexes [Cu(binap)2]+ and [Cu(binap)I]2 with binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl are reported. The lowest-energy excited state of [Cu(binap)2]+ is an IL ππ∗ state of the binaphthyl chromophore. The luminescence of the cation consists of a fluorescence and a phosphorescence originating from this IL state. In contrast, the dimer [Cu(binap)I]2 is characterized by a I  → binap LLCT state which occurs at lower energies than the binap IL state. The dimer shows only a single emission band. This luminescence is suggested to come from the LLCT triplet.
Keywords: Fluorescence; Phosphorescence; Copper(I); Phosphine complexes; LLCT;

4′-Chloro-2,2′:6′,2″-terpyridine (L): ethyl sulfate salts of [H2L]2+ and the single crystal structures of [H2L][EtOSO3]Cl · H2O and [ML2][PF6]2 with M = Fe and Ru by Jonathon E. Beves; Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Silvia Schaffner; Jennifer A. Zampese (1006-1008).
An efficient microwave oven synthesis of [Ru(1)2][PF6]2 is described (1  = 4′-chloro-2,2′:6′,2″-terpyridine); the method has general application to [Ru(tpy)2]2+ derivatives. [Ru(1)2][PF6]2 and [Fe(1)2][PF6]2 are isostructural and crystallize in the tetragonal P 4 ¯ 2 1 c space group. The preparation and characterization of [H2 1][EtOSO3]2 and the crystal structure of [H2 1][EtOSO3]Cl · H2O are also reported.The preparation and characterization of [H2 1][EtOSO3]2 and the crystal structure of [H2 1][EtOSO3]Cl · H2O are reported (1  = 4′-chloro-2,2′:6′,2″-terpyridine); extensive hydrogen bonding dictates both the conformation of the tpy domain and the crystal packing. An efficient microwave oven synthesis of [Ru(1)2][PF6]2 is described; the method has general application for [Ru(tpy)2]2+ derivatives. In the solid state, [Ru(1)2][PF6]2 and [Fe(1)2][PF6]2 are isostructural and crystallize in the tetragonal P 4 ¯ 2 1 c space group.
Keywords: 4′-Chloro-2,2′:6′,2″-terpyridine; Heterocyclic; Coordination; Iron; Ruthenium;

A new polymorph of 4′-tolyl-2,2′:6′,2′′-terpyridine (ttpy) and the single crystal structures of [Fe(ttpy)2][PF6]2 and [Ru(ttpy)2][PF6]2 by Jonathon E. Beves; Paulina Chwalisz; Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Silvia Schaffner; Jennifer A. Zampese (1009-1011).
The solid-state structure of a new polymorph of 4′-tolyl-2,2′:6′,2′′-terpyridine (ttpy) features packing with weak π-stacking and Npyridine···HC interactions between stacks of ttpy molecules. Improved syntheses of [M(ttpy)2][PF6]2 (M = Fe, Ru), and the single crystal structures of solvates of these complexes are reported.Single crystals of a new polymorph of 4′-tolyl-2,2′:6′,2′′-terpyridine (ttpy) have been grown by evaporation of a hexane–ethyl acetate solution of the ligand; the packing features weak π-stacking and Npyridine···HC interactions between stacks of ttpy molecules. Improved syntheses of [M(ttpy)2][PF6]2 (M = Fe, Ru), and the single crystal structures of [Fe(ttpy)2][PF6]2  · 2.2MeCN and [Ru(ttpy)2][PF6]2  · 1.75MeCN · 0.2H2O are reported.
Keywords: 4′-Tolyl-2,2′:6′,2′′-terpyridine; Coordination; Polymorph; Iron; Ruthenium;

Mg7V4O16(OH)2(H2O): A magnesium vanadate with a novel 3D magnesium oxide open framework by Ting Hu; Ji-Bei Lin; Fang Kong; Jiang-Gao Mao (1012-1014).
Hydrothermal reaction of V2O5 and Mg(BO2)2(H2O) in H2O afforded a novel magnesium vanadate with a non-centrosymmetric structure, Mg7V4O16(OH)2(H2O). Its structure features a novel 3D openframe network of magnesium(II) oxide futher decorated by VO4 tetrahedra and 1D chains of face-sharing MgO6 octahedra.Hydrothermal reaction of V2O5 and Mg(BO2)2(H2O) in H 2 O afforded a novel magnesium vanadate with a non-centrosymmetric structure, Mg7V4O16(OH)2(H2O). The structure of Mg7V4O16(OH)2(H2O) features a novel 3D openframe network of magnesium(II) oxide with tunnels along c-axis based on 6- and 12-member rings (MR), the V(2)O4 tetrahedra are located at 6-MR tunnels whereas V(1)O4 tetrahedra and the 1D chains composed of the face-sharing Mg(1)O6 octahedra are located at the 12-MR tunnels.
Keywords: Magnesium vanadate; Crystal structure; Open framework; Acentric structure;

Coordination polymers of cobalt(II) with pyrimidine and pyrazine: Syntheses, structures and magnetic properties by Mikhail A. Kiskin; Grygory G. Aleksandrov; Artem S. Bogomyakov; Vladimir M. Novotortsev; Igor L. Eremenko (1015-1018).
New 2D-polymer [Co2(μ-OH2)(μ-Piv)2(Piv)2(μ-L1)2] n (2) and 3D-polymer [Co5(μ-OH2)(μ3-OH)(μ3-Piv)(μ-Piv)5(Piv)3(μ-L2)4] n (3) have been synthesized and characterized. It was shown that compound 2 undergoes antiferromagnetic ordering with weak ferromagnetism at TN  = 4.5 K with σ 0(2 K) = 4000 G cm3/mol.New 2D-polymeric compound [Co2(μ-OH2)(μ-Piv)2(Piv)2(μ-L1)2] n (2) was synthesized in the reaction of the cobalt(II) pivalate [Co(Piv)2] n (1, Piv is an anion of pivalic acid) and pyrimidine (L1) in MeCN. 3D-polymer [Co5(μ-OH2)(μ3-OH)(μ3-Piv)(μ-Piv)5(Piv)3(μ-L2)4] n (3) was prepared by the reaction of the polymer [Co(Piv)2] n (1) with pyrazine (L2). Complexes 2 and 3 were characterized by the X-ray diffraction and magnetic susceptibility. It was shown that compound 2 undergoes antiferromagnetic ordering with weak ferromagnetism at TN  = 4.5 K with σ 0(2 K) = 4000 G cm3/mol.
Keywords: Polymeric cobalt(II) complex; Carboxylate ligands; X-ray diffraction analysis; Magnetic properties;

Synthesis, EPR and DFT calculations of rare Ag(II)porphyrins and the crystal structure of [Zn(II)tetrakis(4-bromo-2-thiophene)porphyrin] by Mohamed Ghazzali; Morsy A.M. Abu-Youssef; Krister Larsson; Örjan Hansson; Adel Amer; Toomas Tamm; Lars Öhrström (1019-1022).
4-Bromo-2-thiophene and 5-bromo-2-thiophene porphyrins were synthesized in 18% yield and reactions with either Zn(OAc)2  · 2H2O or Ag(OAc) afforded the corresponding metal complexes characterized by IR, NMR, EPR and XPS. The crystal structure of tetra(4-bromo-2-thiophene)porphyrinato Zn(II) shows a zigzag-like packing pattern supported by S···S interactions.Meso-tetrakis (4-bromo-2-thiophene) and (5-bromo-2-thiophene) porphyrins were synthesized in 18% yield from freshly distilled pyrrole and the corresponding aldehydes in refluxing propionic acid. Reaction of both porphyrins with either Zn(OAc)2  · 2H2O or Ag(OAc) afforded the corresponding metal complexes in 20% yield. The free bases and metal complexes were characterized by IR, NMR, EPR, MS and XPS. The crystal structure of 5,10,15,20(4-bromo-2-thiophene)porphyrinato Zn(II) was determined by X-ray diffraction and shows a ‘zigzag-like’ packing pattern due to S···S intermolecular interaction. Structural features of these molecules are discussed by DFT quantum chemical calculations.
Keywords: Porphyrins; Ag(II); X-ray structure determination; DFT; EPR;

Synthesis, structure, and magnetic properties of a new binuclear Ni(II) complex supported by 1,4,8-triazacycloundecane by Piotr L. Pawlak; Aramice Y.S. Malkhasian; Bojan Sjlivic; Matthew J. Tiza; Benjamin E. Kucera; Reza Loloee; Ferman A. Chavez (1023-1026).
A new binuclear nickel(II) complex, [Ni2(tacud)2(μ-H2O)(μ-Cl)2]Cl2 (tacud = 1,4,8-triazacycloundecane), is reported. In this complex, Ni(II) centers are bridged by two chloro and one aqua ligand while terminal positions are capped by tacud ligands. Magnetic studies reveal that the complex is weakly ferromagnetic.A new synthetic binuclear nickel(II) compound ([Ni2(tacud)2(μ-H2O)(μ-Cl)2]Cl2 (1); tacud = 1,4,8-triazacycloundecane) is reported. Compound 1 contains two Ni(II) ions bridged by two chloro and one aqua ligand resulting in a short Ni···Ni distance of 3.0187(10) Å. Each nickel is capped by terminal tacud ligands and possesses distorted octahedral geometry. This compound exhibits a new structural motif for metal complexes supported by tacud. Compound 1 exhibits two solvent dependent transitions in the UV–vis spectrum. Variable temperature SQUID magnetic susceptometry studies on 1 indicate mild ferromagnetism exists at room temperature (μ eff  = 4.78 μB) which increases upon temperature lowering. Magnetic analysis of 1 in the temperature range 2–300 K confirm weakly ferromagnetic behavior with J  = +2.28 cm−1.
Keywords: Macrocyclic ligand; Ni(II); Binuclear complex; X-ray crystallography; UV–vis spectroscopy; SQUID susceptometry;

Microwave assisted synthesis of ferrocene amides by S. Funda Ekti; Deniz Hür (1027-1029).
A new microwave assisted synthesis methodology has been presented for the preparation of the ferrocene amides. Ferrocene carboxylic acid was derivatised using direct BtH/SOCl2 methodology to prepare N-ferrocenoyl benzotriazole as a new starting material for the functionalization of ferrocene.A new microwave assisted synthesis methodology has been presented for the preparation of the ferrocene amides. Ferrocene carboxylic acid was derivatised using direct 1H-Benzotriazole/SOCl2 methodolgy to prepare N-ferrocenoyl benzotriazole as a new starting material for the functionalization of ferrocene ring. N-ferrocenoyl benzotriazole was reacted with mono- and di-amines under microwave irradiation to prepare ferrocene mono- and di-amides in high purity and in good yield.
Keywords: Ferrocene; Ferrocene amide; Benzotriazole; Microwave;

A novel three-dimensional 3d–4f heterometallic coordination polymer: Crystal structure and photoluminescence by Ying-Ying Bai; Yan Huang; Bing Yan; Yi-Shan Song; Lin-Hong Weng (1030-1032).
One novel 3d–4f heterometallic coordination polymer {[ZnEu(PDA)2(BDC)1/2(H2O)] · 2H2O} n (PDA = pyridine-2,5-dicarboxylate, BDC = 1,4-benzenedicarboxylate) has been synthesized by hydrothermal method. PDA ligands with two kinds of coordination modes bridge Eu and Zn centers into two types of 2D layers, which further intersect at Eu centers and form a 3D network. BDC ligands act as a linear bridge inter-layer Eu centers, resulting in the final 3D network.A novel 3d–4f heterometallic coordination polymer {[ZnEu(PDA)2(BDC)1/2(H2O)] · 2H2O} n (PDA = pyridine-2,5-dicarboxylate, BDC = 1,4-benzenedicarboxylate) (1) has been synthesized by hydrothermal method. PDA ligands adopt two kinds of coordination modes to bridge Eu(III) and Zn(II) ions into two types of 2D layers, respectively, which further intersect at Eu(III) ions and form a 3D network. BDC ligands act as a linear linker to bridge the Eu(III) ions from adjacent layers, resulting in the final 3D network. The photoluminescent behavior indicates that the introduction of Zn ions in the 3-D polymeric fragment slightly enhances the luminescent lifetime and quantum efficiency.

A novel μ 6-sulfato hexanuclear cobalt(II) complex, Na2[Co6(Hccdp)3(μ 6-SO4)] · 30H2O (1) was anaerobically synthesized and isolated from the reaction of CoSO4  · 7H2O with ligand H5ccdp (where H5ccdp  =  N,N -Bis[2-carboxybenzomethyl]-N,N -Bis[carboxymethyl]-1,3-diaminopropan-2-ol) in the presence of NaOH in aqueous-acetonitrile solution. The crystal structure of 1 contains a [ Co 6 II ( μ 6 - SO 4 ) ] core unit which is held together by three heptadentate bridging ligands, Hccdp4–. Furthermore, the [ Co 6 II ( μ 6 - SO 4 ) ] core unit is providing a templating and stabilizing factor for the Co6 cluster center.A novel μ 6-sulfato hexanuclear cobalt(II) complex, Na2[Co6(Hccdp)3(μ 6-SO4)] · 30H2O (1) was isolated from the reaction of CoSO4  · 7H2O with ligand H5ccdp (where H5ccdp  =  N,N -Bis[2-carboxybenzomethyl]-N,N -Bis[carboxymethyl]-1,3-diaminopropan-2-ol) in the presence of NaOH in aqueous-acetonitrile solution and its X-ray crystal structure has been determined. The structure of 1 contains a [ Co 6 II ( μ 6 - SO 4 ) ] core unit which is held together by three heptadentate bridging ligands, Hccdp4−.
Keywords: Dinucleating bridging ligand; Cobalt(II) complex; Hexanuclear; Self-assembly; X-ray crystal structure;

Synthesis, characterization and crystal structure of fac-[Re(H2O)(CO)3{Ph2PO(CH2)3OPPh2}]BArF by Sandra Bolaño; Jorge Bravo; Jesús Castro; Soledad García-Fontán; Ma Carmen Marín (1037-1039).
The complex fac-[Re(H2O)(CO)3L]BArF (L = Ph2PO(CH2)3OPPh2; BArF  = [B{3,5-(CF3)2C6H3}4]) has been prepared from the reaction of fac-[Re(O3SCF3)(CO)3L] with NaBArF. The compound is not soluble in water and it is stable in solid state as well as in solution of polar organic solvents.The complex fac-[Re(H2O)(CO)3L]BArF (L = Ph2PO(CH2)3OPPh2; BArF  = [B{3,5-(CF3)2C6H3}4]) is prepared from the reaction of fac-[Re(O3SCF3)(CO)3L] with NaBArF in dichloromethane solution. The complex is characterized spectroscopically and its crystal structure is studied by X-ray diffractometry. The spectroscopic features are consequent with the fac configuration shown by the X-ray crystallographic analysis of the solid complex.
Keywords: Rhenium complexes; Aquacarbonyl complexes; Phosphinite ligands;

Catalytic reduction of hydrazine to ammonia by a high-oxidation state molybdenum complex by Heron Vrubel; Vitor Hugo Cardozo Verzenhassi; Shirley Nakagaki; Fábio Souza Nunes (1040-1043).
[MoO2(acac)2] (acac = acetylacetonate) promotes the disproportionation of hydrazine in THF solutions. The active catalytic species, [MoVIO2]2+, are produced according to the reaction: [MoO2(C5H7O2)2] + 2N2H4  → [MoO2]2+  + 2C5H8N2  + 2OH + 2H2O. The main product of the reduction of hydrazine is ammonia while 3,5-dimethylpyrazole (C5H8N2) was isolated as a side-product. A catalytic cycle was proposed and the probable reaction intermediate is a hydrazido-complex, [MoIV =NNH2(OH2)2]2+.[MoO2(acac)2] (acac = acetylacetonate) promotes the disproportionation of hydrazine in THF solutions. The active catalytic species, [MoVIO2]2+, are produced according to the reaction: [MoO2(C5H7O2)2] + 2N2H4  → [MoO2]2+  + 2C5H8N2  + 2OH  + 2H2O. The main product of the reduction of hydrazine is ammonia while 3,5-dimethylpyrazole (C5H8N2) was isolated as a side-product. A catalytic cycle was proposed and the probable reaction intermediate is a hydrazido-complex, [MoIV =NNH2(OH2)2]2+. The intermediate species, [MoVIO2NH3]2+ reacts with hydroxide ion leading to the complex cis-[MoVIO2(OH)2(NH3)], which was isolated and characterized.
Keywords: Hydrazine; Catalysis; Molybdenum; Nitrogenase;

The chelating modes of the ligands around the Cu(II)/Ni(II) centers are the same. They act as pentadentate ligands to metal ions with bidentate to the central metal ion and tridentate to the adjacent terminal metal ions. The steric effects of the N-acyl groups can influence the structure of the trinuclear Ni(II) complexes from linear to bent.Two bent trinuclear Cu(II)/Ni(II) complexes [Cu3(L1)2(py)2] (1) and [Ni3(L2)2(py)4] · DMF (2), where H3L1  =  N-(3,5-dimethylbenzoyl)-5-bromosalicylhydrazide, H3L2  =  N-(3,5-dimethyl benzoyl)-salicylhydrazide, were synthesized and structurally characterized. In complex 1, all three Cu(II) ions take distorted planar square geometry, while in complex 2, the two terminal Ni(II) ions are distorted planar square, the central Ni(II) ion is octahedral. The magnetism of complex 1 was also studied.
Keywords: Trinuclear; Bent; X-ray structure; Magnetism;

Redox responsive luminescent switch based on a ruthenium(II) complex [Ru(bpy)2(PAIDH)]2+ by Yi-Xian Yuan; Yu Chen; Yi-Can Wang; Cheng-Yong Su; Si-Min Liang; Hui Chao; Liang-Nian Ji (1048-1050).
A new ruthenium(II) polypyridine complex [Ru(bpy)2(PAIDH)]2+ exhibits electrochemically “off–on” luminescent switch through exchanging two protons and two electrons between the quinone/hydroquinone redox couple at room temperature.A new ruthenium(II) polypyridine complex, [Ru(bpy)2(PAIDH)]2+ (1) (bpy = 2,2′-bipyridine; PAIDH = 2-pyridyl-1H-anthra[1,2-d]imidazole-6,11-dione) has been found to display electrochemically “off–on” luminescent switch through exchanging two protons and two electrons between the quinone/hydroquinone redox couple at room temperature.
Keywords: Ruthenium complexes; Redox; Luminescent switch;

Crystallography and photoluminescence properties of β-diketonate monoporphyrinate ytterbium(III) complexes by Hongshan He; Andrew G. Sykes; David Galipeau; Seik Weng Ng; Michael Ropp (1051-1053).
The ytterbium(III) ions in β-diketonate monoporphyrinate ytterbium(III) complexes were seven-coordinate with one solvent molecule (water or methanol), which quenches the near-infrared emission of ytterbium(III) lanthanide dramatically.The structures of two β-diketonate monoporphyrinate ytterbium(III) complexes were characterized by single-crystal X-ray diffraction analysis revealing, for the first time, seven-coordinate Yb(III) metal centers. The results reveal that there is only one solvent molecule (water or methanol) coordinating to ytterbium(III) in the complexes. Their photoluminescence of complexes in solution also shows that water and methanol that bind to ytterbium(III) ion quench the near-infrared emission of lanthanide, resulting a shorter lifetime (∼2.4 μs).
Keywords: Porphyrin; Lanthanide; Near-infrared; Emission; β-Diketonate;

The one-pot synthesis and the fluorescence and cytotoxicity studies of chlorotricarbonyl(α-diimine)rhenium(I), fac-(CO)3(α-diimine)ReCl, complexes by Dejene K. Orsa; Gregory K. Haynes; Saroj K. Pramanik; Maurice O. Iwunze; George E. Greco; Douglas M. Ho; Jeanette A. Krause; Dwayne A. Hill; Richard J. Williams; Santosh K. Mandal (1054-1056).
Luminescent chlorotricarbonyl(α-diimine)rhenium(I) complexes exhibit cytotoxicity against numerous cancer cell lines.An one-pot reaction of Re2(CO)10 and an α-diimine (1:2 molar ratio) in refluxed 2-chloroethanol afforded the corresponding chlorotricarbonyl(α-diimine)rhenium(I) complexes, fac-(CO)3(α-diimine)ReCl, 1-4, in very high yield. The α-diimines in 1-4 are 2,2′-bipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, respectively. Alternatively, an one-pot reaction of Re2(CO)10 and an α-diimine (1:2 mole ratio) in refluxed 1-pentanol in the presence of CO2 and HCl yielded the corresponding chloro complexes, 1-4, in very high yield. 1-4 were characterized spectroscopically. Additionally, 3 and 4 were characterized through X-ray crystal structure determinations. The chloro complexes, 1-4 exhibit fluorescence both in the solid states and in solutions. Surprisingly, 1-4 are cytotoxic against breast, prostate, and lung cancer cell lines.
Keywords: Rhenium; Chloride; Crystal structure; Fluorescence; Cancer cell lines;

A novel lanthanide oxalatophosphonate with a 3D open–framework structure, [Gd2{HO3PCH2NHCH2(CH2CH2OPO2)}(C2O4)2.5(H2O)2] · 5H2O 1 has been synthesized by hydrothermal technique, using organophosphonic acid, H2O3PCH2NCH2(CH2CH2OPO2H) as ligand, and oxalate as the second ligand. The interconnection of gadolinium (Ш) by bridging H2L anions leads to a 3D open-framework structure with channels along the a-axis. The channel is formed by 44-membered rings composed of six gadolinium (Ш) ions and six H2L anions. The chelating and bridging oxalates are found on the surface of the channels extending along the a direction.A novel lanthanide oxalatophosphonate, [Gd2{HO3PCH2NHCH2(CH2CH2OPO2)}(C2O4)2.5(H2O)2] · 5H2O 1 has been synthesized by hydrothermal reaction at 140 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The interconnection of gadolinium(Ш) ions by bridging H2L anions leads to a 3D open-framework structure with channels along the a-axis. The channel is formed by 44-membered rings composed of six gadolinium(Ш) ions and six H2L anions. The chelating and bridging oxalates are found on the surface of the channels extending along the a direction.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Gadolinium(III);

Mono- and di-nuclear 2,3-diazabutadiene and 2-azabutadiene complexes of Rhenium(I): Syntheses, luminescence spectra and X-ray structures by Rodolphe Kinghat; Abderrahim Khatyr; Gerard Schmitt; Michael Knorr; Marek M. Kubicki; Estelle Vigier; Fernando Villafañe (1060-1063).
The di-nuclear complexes [(OC)3Re(μ-Ph2C=N–N=CPh2)(μ-X)2Re(CO)3] (X = Br, Cl), which represent the first examples of benzophenone azine-bridged complexes, have been prepared. Nucleophilic attack of NaSPh on [Cl2C=C(H)–N=CPh2] affords the 2-azabutadiene derivative [(PhS)(Cl)C=C(H)–N=CPh2], which upon reaction with [Re(CO)3(THF)(μ-Br)]2 forms the luminescent S,N-chelate complex fac-[(OC)3ReBr{(PhS)(Cl)C=C(H)–N=CPh2}].Treatment of [Re(CO)3(THF)(μ-Br)]2 with 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene [Cl2C=C(H)–N=CPh2] (1a) yields the di-nuclear benzophenone azine-bridged compound [(OC)3Re(μ-Ph2C=N–N=CPh2)(μ-Br)2Re(CO)3] (2a), albeit in low yield. Alternatively, compounds [(OC)3Re(μ-Ph2C=N–N=CPh2)(μ-X)2Re(CO)3] (2a,b) (X = Br, Cl) are obtained in high yields by direct reaction of [Re(CO)3(THF)(μ-Br)]2 or [Re(CO)5Cl] with benzophenone azine. Nucleophilic attack of NaSPh on 1a affords the 2-azabutadiene derivative [(PhS)(Cl)C=C(H)–N=CPh2] (1b), which upon reaction with [Re(CO)3(THF)(μ-Br)]2 forms the S,N-chelate complex fac-[(OC)3ReBr{(PhS)(Cl)C=C(H)–N=CPh2}] (3). The crystal structures of 1b, 2a and 3 have been determined and the luminescence properties of 2 and 3 have been investigated.
Keywords: 2-Azabutadiene; 2,3-Diazabutadiene; Azine; Thioether; Rhenium; Luminescence;

A water-soluble molecular precursor [Sr(H2O)]7[Ti(O2)(edta)] · H2O (1) was used for the preparation of stoichiometric SrTiO3, which was synthesized from the reaction of [Ti(H2O)(edta)], H2O2 and Sr(NO3)2  · 6H2O at pH range of 4.0 –5.0.A well-characterized strontium edta complex [Sr(H2O)]7[Ti(O2)(edta)] · H2O (1) was synthesized from the reaction of [Ti(H2O)(edta)], H2O2 and Sr(NO3)2  ·  6H2O at pH 4.0–5.0 (H4edta = ethylenediaminetetraacetic acid), which is used as a molecular precursor for the preparation of stoichiometric SrTiO3.
Keywords: Titanate; Single molecular precursor; Water clusters; Crystal structure;

An abnormal 8-fold [4 + 4] interpenetrating diamond network is formed through strong hydrogen bonds connected unusual supramolecular tetrahedral building units, which are defined by the coordination of two 2,2′-bipy ligands and two carboxylate groups around Zn(II).A new complex with a hydrogen-bonded diamond network, [Zn(2,2′-bipy)2(HBBDC)2] (1) has been synthesized by the assembly of H2BBDC, Zn(II) and 2,2′-bipy (H2BBDC = bibenzyl-4,4′-dicarboxylic acid and 2,2′-bipy = 2,2′-bipyridine). The coordination of two 2,2′-bipy ligands and two carboxylate groups around Zn(II) interplays with the hydrogen-bonding involving the deprotonated and protonated carboxylate, making the mononuclear molecule an unusual supramolecular tetrahedral building unit for the diamond network. The long bridging ligand leads to 8-fold interpenetration of the net in the abnormal [4 + 4] mode. Compound 1 shows a strong fluorescent emission at 400 nm in solid state at room temperature.

Representation of the [Er(H2L)(NO3)] mononuclear erbium unit obtained from N,N′-bis[(2-salicylideneamino)ethyl]ethane-1,2-diamine N4O2 hexadentate Schiff base.Solvothermal synthesis led to a novel Er complex with N,N′-bis[(2-salicylideneamino)ethyl]ethane-1,2-diamine. Its crystal structure can be described by [Er(H2L)(NO3)] units in which Er atom is surrounded with a N4O2 Schiff base and a bidentate NO 3 - group. These units are linked together by hydrogen bonds through H2O to build infinite chains.
Keywords: Lanthanide complexes; Schiff base; Solvothermal synthesis; Crystal structure;

Complexes [Ln(dotpH7)(H2O)2]Cl2  ·  xH2O (1·Ln) (Ln = La, Nd, Sm, Eu, Gd, Tb) and [Ln(dotpH7)(H2O)2](ClO4)2  ·  xH2O (2·Ln) (Ln = Nd, Sm, Eu, Gd, Tb) [dotpH8  = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis-(methylenephosphonic acid)] show chain structures with interesting catalytic and luminescent properties.Based on 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis-(methylenephosphonic acid) (dotpH8), compounds [Ln(dotpH7)(H2O)2]Cl2  ·  xH2O (1·Ln) (Ln = La, Nd, Sm, Eu, Gd, Tb) and [Ln(dotpH7)(H2O)2](ClO4)2  ·  xH2O (2·Ln) (Ln = Nd, Sm, Eu, Gd, Tb) are synthesized in aqueous solutions at low pH. Compounds within each kind are isostructural. Both show chain structures where the neighboring {LnO8} polyhedra are doubly bridged by {CPO3} tetrahedra through corner-sharing. The packing of chains, however, are different in the two cases. In 1·Ln, each chain is surrounded by six equivalent chains, with the Cl counterions and the lattice water molecules locating between the chains. In 2·Ln, neighboring chains are connected via strong hydrogen bond interactions to form a supramolecular layer in the ab plane. The ClO 4 - counterions fill in the inter-layer spaces. The catalytic and luminescent properties are investigated.
Keywords: Lanthanide; Polyazamacrocycle; Phosphonate; Catalytic property; Crystal structure;

Anion-dependent structural diversity in cadmium coordination polymers of flexible bis(1,2,4-triazol-1-yl)butane by Jiangang Ding; Xungao Liu; Baolong Li; Liyan Wang; Yong Zhang (1079-1081).
Anion-dependent four Cd(II) coordination polymers 1D chain [Cd(btb)(H2O)2(NO3)2] n (1), threefold interpenetrated diamondoid network {[Cd(btb)2(H2O)2](BF4)2} n (2), threefold interpenetrated α-polonium cubic network {[Cd(btb)3](ClO4)2} n (3) and {[Cd(btb)3](PF6)2} n (4) were synthesized using the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane (btb). Compounds 1, 2, 3 and 4 exhibit blue luminescent emissions maxima at 439, 426, 422 and 424 nm, respectively, in the solid state at room temperature. The frameworks of 2, 3, 4 maintain stable up to 240 °C.The self-assembly reactions of the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and Cd(II) salts with different anions NO 3 - , BF 4 - , ClO 4 - , PF 6 - give 1D chain [Cd(btb)(H2O)2(NO3)2] n (1), threefold interpenetrated diamondoid network {[Cd(btb)2(H2O)2](BF4)2} n (2), threefold interpenetrated α-polonium cubic network {[Cd(btb)3](ClO4)2} n (3) and {[Cd(btb)3](PF6)2} n (4). Compounds 1, 2, 3 and 4 exhibit blue luminescent emission maxima at 439, 426, 422 and 424 nm, respectively, in the solid state at room temperature. The frameworks of 2, 3, 4 maintain stable when 2, 3, 4 are kept at 240 °C at vacuum for 2 h.
Keywords: Anion role; Coordination polymer; Cadmium complex; Bis(12,4-triazol-1-yl)butane; Luminescence;

Substitution reactions of Fe and Ru complexes with liquid phosphite ligands in the absence of solvents by Apollinaire Munyaneza; Muhammad D. Bala; Neil J. Coville (1082-1084).
The substitution reactions of solid piano-stool Fe and Ru complexes have been carried out with liquid phosphite ligands that also acts as ‘solvents’ for the reaction. The reagent Me3NO · 2H2O has been shown to be a good decarbonylating agent for the solvent-free reaction.The substitution reactions of solid piano-stool Fe and Ru complexes have been carried out with liquid phosphite ligands that also act as ‘solvents’ for the reaction. It was observed that the solvent-free reaction occurs more slowly than the corresponding reaction in a solvent. Addition of a catalyst, [CpFe(CO)2]2, did result in a more rapid substitution reaction but again the reaction was slower in the absence of a solvent. The reagent Me3NO · 2H2O has been shown to be a good decarbonylating agent for the solvent-free reaction.
Keywords: Substitution reactions; Iron; Liquid phosphites; Solventless chemistry;

A novel inclusion complex form between Q[10] host and Q[5] guest stabilized by potassium ion coordination by Jing-Xin Liu; Rui-Lian Lin; La-Sheng Long; Rong-Bin Huang; Lan-Sun Zheng (1085-1087).
A novel inclusion complex was synthesized via a self-produced intermediate template route. The X-ray crystallography shows a inner capsule is encapsulated in a larger macrocycle Q[10] and Q[10] is stabilized by intermediate template.A novel inclusion complex H 2 O @ Q [ 5 ] K 2 2 + @ Q [ 10 ] Cl 2 ( HCl ) ( H 2 O ) 37 was synthesized via a self-produced intermediate template route. The X-ray crystallography shows two potassium cations coordinated to each portal of Q[5] to form closed molecular capsule, in which a water molecule was encapsulated. Interestingly, the closed molecular capsule is trapped in the cavity of a bigger macrocycle Q[10] and the inclusion complex is stabilized by potassium ion coordination. The structure of the inclusion complex was further confirmed by 1H NMR spectra and X-ray photoelectron spectra (XPS). Possible formation process of the title complex was proposed based on the experiment results.
Keywords: Cucurbit[n]uril; Inclusion complex; X-ray crystallography; 1H NMR and XPS analysis;

Synthesis, crystal structure and spectroscopic properties of a new chiral cadmium (II) malate by Adel Beghidja; Chahrazed Beghidja; Guillaume Rogez; Pierre Rabu; Richard Welter (1088-1090).
A new chiral 3D covalent polymer based on chiral bridging ligands, the coordination environment around the CdII being pentagonal bipyramidal.A new chiral 3D metal-organic coordination polymer [Cd((S)-mal)] (mal = malic acid), has been solvothermally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Colorless crystals crystallize in the orthorhombic system, space group P212121, a  = 6.804(1), b  = 8.488(2), c  = 9.997(3) Å, V  = 577.35 (2) Å3, Z  = 4 and R 1  = 0.0298. The structure of the compound exhibits a chiral 3D covalent framework based on chiral bridging ligands, the coordination environment around the CdII is pentagonal bipyramidal.
Keywords: Malate ligands; Coordination polymer; Chirality; Cadmium; Hydrothermal synthesis;

A new sodium coordination polymer with benzene-1,2,4-tricarboxylic acid, [Na3(btc)(H2O)2] · 2H2O was prepared by crystallization from DMF solution. The unusual non-centrosymmetric structure contains four crystallographically independent metal centers with six-coordination configuration. Carboxylate oxygen atoms and water molecules bridge the adjacent Na atoms to form a polymeric network. The three-dimensional network contains almost ellipsoidal channels occupied by the uncoordinated water molecules.A new sodium coordination polymer with benzene-1,2,4-tricarboxylic acid, [Na3(btc)(H2O)2] · 2H2O was prepared by crystallization from DMF solution and characterized by IR, single-crystal X-ray and thermal analyses. The non-centrosymmetric structure contains four crystallographically independent metal centers with six-coordination configuration. Carboxylate oxygen atoms and water molecules bridge the adjacent Na atoms to form a polymeric network. The three-dimensional network contains of almost ellipsoidal channels occupied by the uncoordinated water molecules. On heating, the complex loses water molecules, immediately forming a stable anhydrous compound. The features of IR spectrum are clearly compatible with the structural characteristics of the complex under study.
Keywords: Sodium benzene-12,4-tricarboxylate; Crystal structure; Coordination polymer; TG;

1D tubular and 2D roof-like coordination polymers based on [Zn(Pdc)] helices: Syntheses, structures and photoluminescence by Jun He; Gui-Ping Tan; Jing-Xiang Zhang; Yan-Na Zhang; Ye-Gao Yin (1094-1096).
Parallel reactions of 2,5- and 2,6-pyridinedicarboxylic acids with 3,3′, 5,5′-tetramethyl-4,4′-bipyrazole and ZnSO4 afforded two novel coordination polymers, 1 (left) and 2 (right), noteworthy of containing the [Zn(Pdc)]n helices as building blocks.By parallel hydrothermal reactions of 2,5-pyridinedicarboxylic acid (2,5-H2Pdc) and 2,6-pyridinedicarboxylic acid (2,6-H2Pdc) with 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (Bpz) and ZnSO4  · 7H2O, two novel zinc coordination polymers, [Zn(Bpz)(2,5-Pdc)] n (1) and [Zn 2 (Bpz)(2,6-Pdc) 2 ] n (2), which contain in situ formed [Zn(Pdc)] n helices as building blocks and exhibit photoluminescent at room temperature, were synthesized respectively.
Keywords: Zinc coordination polymer; Helix; Crystal structure; Photoluminescence;

The reaction of 2-phenylazopyridine (pap) ligand with [Ru(bpy)(CO)Cl2]2 results in the formation of [Ru(bpy)(pap)ClX]+ (X = CO or CH3CN) complexes. The structures of the [Ru(bpy)(pap)Cl(CO)]PF6 and [Ru(bpy)(pap)Cl(CH3CN)]PF6 complexes were determined by single crystal X-ray diffraction studies. The complexes had different configurations with regard to the pap ligand.The reaction of an asymmetrical bidentate 2-phenylazopyridine (pap) ligand with a ruthenium carbonyl dimer ([Ru(bpy)(CO)Cl2]2; bpy = 2,2′-bipyridine) results in cleavage of the chloro bridge and the formation of cationic [Ru(bpy)(pap)ClX]+ complexes. In addition to spectroscopic characterization, the structures of the [Ru(bpy)(pap)Cl(CO)]PF6 and [Ru(bpy)(pap)Cl(CH3CN)]PF6 complexes were determined by single crystal X-ray diffraction studies. The structurally characterized complexes had different configurations with regard to the pap ligand. The coligands (CO and CH3CN) play an important role in the incorporation of the asymmetrical bidentate ligand.
Keywords: Ruthenium; Azopyridyl ligand; Crystal structure; Carbonyl complex; Acetonitrile complex;

A 1D chain single-μ-chloro bridged Cu(II) complex (CuLRRCl2) n (LRR  = (−)-4,5 pinene bipyridine) (1) was successfully synthesized and characterized by X-ray crystallography and magnetic measurements. The structure of 1 is a one-dimensional infinite chain polymer, while the magnetic investigations demonstrate that 1 exhibits intrachain Cu(II)–Cu(II) antiferromagnetic interaction with J  = −2.276 cm−1.Using chiral bidentate ligand containing N-donors LRR (−)-4,5 pinene bipyridine, a 1D chain single-μ-chloro bridged Cu(II) complex (CuLRRCl2) n (1) was synthesized in methanol and characterized by X-ray crystallography and magnetic measurements. X-ray analysis shows that 1 crystallizes in space group Pbca of orthorhombic. The structure of 1 is a neutral, one-dimensional infinite chain polymer. The magnetic investigations demonstrate that complex 1 exhibits intrachain Cu(II)–Cu(II) antiferromagnetic coupling with J  = −2.276 cm−1.
Keywords: Chain; Chloro bridge; Copper; Crystal structure; Magnetic property;

New homoleptic carbene transfer ligands and related coinage metal complexes by Grazia Papini; Giuliano Bandoli; Alessandro Dolmella; Giancarlo Gioia Lobbia; Maura Pellei; Carlo Santini (1103-1106).
The synthesis, spectroscopic and structural characterization of the carbene ligand precursor bis(4-benzyl-1,2,4-triazol-4-ium-1-yl)dihydroborate has been described. Treatment with Ag2O leads to the silver(I) complex of the new monoanionic bis(4-benzyl-1,2,4-triazol-5-ylidene-1-yl)dihydroborate dicarbene ligand. The resulting dimetallacycle carbene complex has been used to synthesize the homoleptic gold(I) complex by transmetallation reaction.The synthesis, spectroscopic and structural characterization of the carbene ligand precursor bis(4-benzyl-1,2,4-triazol-4-ium-1-yl)dihydroborate has been described. Treatment with Ag2O leads to the silver(I) complex of the new monoanionic bis(4-benzyl-1,2,4-triazol-5-ylidene-1-yl)dihydroborate dicarbene ligand. The resulting dimetallacycle carbene complex has been used to synthesize the homoleptic gold(I) complex by transmetallation reaction.
Keywords: Scorpionates; Silver(I); Gold(I); 1,2,4-Triazole; N-Heterocyclic carbenes; X-ray; Spectroscopy;