Inorganic Chemistry Communications (v.10, #7)

Contents List (iii-x).

Reaction of [Cu(AcO)2(H2O)]2 with pyridine-terminated polydimethylsiloxane (PDMS) yields 1 as a green oil. PDMS chains are effective solubilising groups affording 1 a solubility of ca. 1.7 mM in scCO2, whilst related copper derivatives are insoluble.Pyridine-terminated polydimethylsiloxane (PDMS) was synthesised by hydrosilylation of 4-vinylpyridine with hydride terminated PDMS. The product obtained was a mixture of both the Markovnikoff and anti-Markovnikoff products. Reaction with [Cu(AcO)2(H2O)]2 in ethanol, yielded 1, isolated as a green oil. Compound 1 contained 4–6% copper by weight indicating that some terminal pyridines remained uncoordinated. Solubility studies of 1 in supercritical carbon dioxide (scCO2) demonstrated the effectiveness of PDMS chains as solubilising groups. Whilst 1 showed a solubility ca. 1.7 mM in scCO2, related copper derivatives were observed to be insoluble.
Keywords: Copper complexes; Polydimethylsiloxane; Supercritical carbon dioxide;

Novel coordination mode of chloride ion in holo- and hemidirected one-dimensional PbII coordination polymer by Nader Noshiranzadeh; Ali Ramazani; Ali Morsali; Allen D. Hunter; Matthias Zeller (738-742).
A new lead(II) chloride coordination polymer with the ligand 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (pyterpy), [Pb3(pyterpy)22-Cl)33- Cl)3] n  ·  nMeOH, has been synthesized and structurally analyzed by X-ray single-crystal diffraction. Its single-crystal X-ray structure shows the complex is one-dimensional polymer as a result of chloride unusual bi- and tridonor bridging and also shows three types of Pb2+-ions with coordination numbers of six (Pb1 and Pb2) and eight Pb3. The Pb1 and Pb3 centers possess the coordination sphere of holodirected. However, the arrangement of Cl- and N-atoms for Pb2 suggests a gap or hole in the coordination geometry around this atom and its coordination sphere is, thus, hemidirected.A new lead(II) chloride coordination polymer with the ligand 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (pyterpy), [Pb3(pyterpy)22-Cl)33-Cl)3] n  ·  nMeOH, has been synthesized and structurally analyzed by X-ray single-crystal diffraction. Its single-crystal X-ray structure shows the complex is one-dimensional polymer as a result of chloride unusual bi- and tri-fold donor bridging and also shows three types of Pb2+-ions with coordination numbers of six (Pb1 and Pb2) and eight Pb3. The Pb1 and Pb3 centers possess the coordination sphere of holodirected. However, the arrangement of Cl- and N-atoms for Pb2 suggests a gap or hole in the coordination geometry around this atom and its coordination sphere is, thus, hemidirected.

Ferrocenyl(dimethyl)aluminum dimer [(η5-C5H5)Fe(η5-C5H4)AlMe2]2 by Bernd Wrackmeyer; Elena V. Klimkina; Tamara Ackermann; Wolfgang Milius (743-747).
The dimer of dimethyl(ferrocenyl))aluminum was prepared and fully characterised in solution and in the solid state for the first time. This dimer contains the ferrocenyl group in a fairly unsymmetrical bridging position: Al(1)–C(1) = 204.6(5) and Al(1)–C(1A) = 226.9(4) pm).The reaction of ferrocenyllithium (FcLi, 1) with dimethyl or diethylaluminum chloride affords known mixed dimers 2 built from dialkyl(ferrocenyl))aluminium and dialkylaluminum chloride and also, depending on the reaction conditions, the unknown dimers from dialkyl(ferrocenyl)aluminum 3, of which the dimethyl derivative could be isolated in a pure state and characterised by X-ray structural analysis. The ferrocenyl group occupies the bridging position and there is a centre of inversion. The solution-state structures were determined by NMR spectroscopic methods (1H, 13C, 27Al NMR). The gas-phase structure of monomer FcAlH2 3(M) was optimised at the B3LYP/6-311 + G(d,p) level of theory.
Keywords: Ferrocene; Aluminum; NMR; X-ray; DFT calculation;

Study of the cytotoxic activity of alkenyl-substituted ansa-titanocene complexes by Santiago Gómez-Ruiz; Goran N. Kaluđerović; Dorian Polo-Cerón; Sanjiv Prashar; Mariano Fajardo; Željko Žižak; Zorica D. Juranić; Tibor J. Sabo (748-752).
Four ansa-titanocene dichloride derivatives were studied in cytotoxic activity in tumour cell lines human adenocarcinoma HeLa, human myelogenous leukemia K562, human malignant melanoma Fem-x and normal immunocompetent cells.The cytotoxic activity on tumour cell lines, human adenocarcinoma HeLa, human myelogenous leukemia K562, human malignant melanoma Fem-x and normal immunocompetent cells, was tested for four different ansa-titanocene dichloride derivatives with potentially reactive substituents [Ti{Me(CH2 =CH)Si(η5-5Me4) (η5-C5H4)}Cl2] (1), [Ti{Me(H)Si(η5-C5Me4)2}Cl2] (2), [Ti{Me{(CH2 =CH)Me2SiCH2CH2}Si(η5-C5Me4)(η5-C5H4)}Cl2] (3) and [Ti{Me2Si(η5-C5Me4)(η5-C5H3(CMe2(CH2CH2CH=CH2)))}Cl2] (4), showing a very promising activity and opening up the possibility of extensive investigation in this field.
Keywords: ansa-Titanocene compounds; Antitumoural activity; Adenocarcinoma HeLa; Human myelogenous leukemia K562; Human malignant melanoma Fem-x;

Two microporous metal–organic frameworks have been assembled by tpt and bdc. The frameworks consist of Cu(I)/Zn(II)-tpt zigzag chains and 1,4-benzenedicarboxylate bidentate bridge. The Zn(II) complex exhibits intriguing hexagonal nano-channels.Two novel metal–organic frameworks, [Cu(tpt)(bdc)1/2] n  ·  nH2O (1) and [Zn(tpt)(bdc)1/2I] n (2) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine, H2bdc = 1,4-benzenedicarboxylic acid), have been prepared by hydrothermal reactions. In complex 1, Cu(I) center is in a trigonal coordination environment with bidentate tpt coordinating Cu(I) atoms to form 1D zigzag chains, and bdc ligand links the zigzag chains to form a 2D layered structure. In complex 2, Zn(II) center is in a trigonal–pyramidal environment with bidentate tpt coordinating Zn(II) atoms to form zigzag chains, and bdc links the zigzag chains to form metal–organic framework which contains interesting hexagonal nano-channels.
Keywords: Cu(I)/Zn(II) complex; metal–organic framework; Crystal structure; 2,4,6-Tris(4-pyridyl)-1,3,5-triazine; 1,4-Benzenedicarboxylate;

Synthesis and crystal structures of two new inorganic–organic hybrid polyoxomolybdate complexes: [Himi]4[{Co(imi)2(H2O)2}Mo7O24] · 4H2O and [Zn(imi)4]2[(imi)2Mo8O26] · 6H2O by Cui-hua Tian; Zhen-gang Sun; Jing Li; Xue-fang Zheng; Hai-dong Liang; Lan-cui Zhang; Wan-sheng You; Zai-ming Zhu (757-761).
The two new inorganic–organic hybrid polyoxomolybdate complexes [Himi]4[Co(imi)2(H2O)2][Mo7O24] · 4H2O (1) and [Zn(imi)4]2[(imi)2 Mo8O26] · 6H2O (2) (imi = imidazole) have been prepared by conventional aqueous solution synthesis and characterized by elemental analyses, IR spectra, TG analysis and single crystal X-ray structural analysis.The two new inorganic–organic hybrid polyoxomolybdate complexes [Himi]4[{Co(imi)2(H2O)2}Mo7O24] · 4H2O (1) and [Zn(imi)4]2[(imi)2Mo8O26] · 6H2O (2) (imi = imidazole) have been prepared by conventional aqueous solution synthesis. Compound 1 consists of heptamolybdate anions [Mo7O24]6− covalently linked by [CoN2O4]2+ octahedra into one-dimensional zigzag-shaped chains. The zigzag-shaped chains are further linked together via the hydrogen-bonding interactions to form a 2D supramolecular framework. Compound 2 is build up of an imidazole-coordinated octamolybdate anion, two imidazole coordinating zinc cations and lattice water molecules to form a three-dimensional framework via complex hydrogen-bonding.
Keywords: Polyoxomolybdate; Zinc; Cobalt; Imidazole;

The air and moisture stable triphenylphosphine (PPh3) adducts of cyclopalladated ferrocenylimidazoline complexes 2a and 2b have been synthesized and structurally characterized by single crystal X-ray diffraction. The catalytic studies on 2a and 2b indicate that they are potent catalysts for the Suzuki reaction of aryl chlorides with phenylboronic acid in neat water under air atmosphere.The air and moisture stable triphenylphosphine (PPh3) adducts of cyclopalladated ferrocenylimidazoline complexes 2a and 2b have been synthesized and structurally characterized by single crystal X-ray diffraction. The catalytic studies on 2a and 2b indicate that they are effective catalysts for the Suzuki reaction of activated aryl chlorides with phenylboronic acid in neat water under air atmosphere.
Keywords: Suzuki coupling; Cyclopalladated ferrocenylimidazolines; Triphenylphosphine adducts; Aryl chlorides; Boronic acids; Neat water;

Synthesis, crystal structure and luminescence of novel two-dimensional interpenetrating frameworks by Feng Li; Yanlong Wang; Guosong Li; Yaguang Sun; Xiaofu Gu; Enjun Gao (767-771).
Two novel metal coordination polymers, [Zn(nic)(isonic)] n (1) and [Cu(nic)(isonic)] n (2) (H2nic = nicotinic acid, H2isonic = isonicotinic acid), have been hydrothermally synthesized. In 1 and 2, two-dimensional interpenetrating (4, 4) frameworks were bridged by nic and isonic ligands, and further assembled into three-dimensional supramolecular structures via a π–π stacking interaction.Two novel metal coordination polymers, [Zn(nic)(isonic)] n (1) and [Cu(nic)(isonic)] n (2) (H2nic = nicotinic acid, H2isonic = isonicotinic acid), have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. X-ray single-crystal structural analyses reveal that 1 and 2 are isomorphous, two-dimensional interpenetrating (4, 4) frameworks bridged by nic and isonic ligands, and further assembled into a three-dimensional supramolecular structure via π–π stacking interaction. Moreover, 1 displayed photoluminescent properties in the blue range at room temperature.
Keywords: Hydrothermal synthesis; Coordination polymers; Crystal structural; Interpenetration;

A series of new diamide ligands were introduced into the complexes of Eu(NO3)3 and Tb(NO3)3 so as to improve the fluorescent properties. The fluorescent properties of the resulting complexes were investigated. It was found that the complexes subject to the excitation of UV light showed characteristic emission of europium and terbium ions, in particular, the Tb complexes had very much intense fluorescence.A series of new diamide ligands were introduced into the complexes of Eu(NO3)3 and Tb(NO3)3 so as to improve the fluorescent properties. The fluorescent properties of the resulting complexes were investigated. It was found that the complexes subject to the excitation of UV light showed characteristic emission of europium and terbium ions, in particular, the Tb complexes had very much intense fluorescence.
Keywords: Diamide ligand; Eu and Tb complexes; Fluorescent properties;

Supramolecular assembly of 1,3-diaminopropane and its unusual conversion by macrocyclic nickel(II) complex by Yan-Hui Su; Jie Liu; Jia Li; Tie-Peng Zhao; Jian-Wei Li; Yu Zhu (776-778).
The reaction of macrocyclic nickel(II) complex [NiL](ClO4)2 (1) with 1,3-diaminopropane affords a novel complex with the formula [NiL(a.a.)2](ClO4)2 (2), where L  = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, a.a. = H3N+(CH2)4COO(5-aminovaleric acid ion), which reveals that the organic ligand 1,3-diaminopropane is converted during the process of the reaction.The reaction of macrocyclic nickel(II) complex [NiL](ClO4)2 (1) with 1,3-diaminopropane affords a novel complex with the formula [NiL(a.a.)2](ClO4)2 (2), where L  = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, a.a. = H3N+(CH2)4COO(5-aminovaleric acid ion), which reveals that the organic ligand 1,3-diaminopropane is converted during the process of the reaction.
Keywords: Ligand conversion; Macrocyclic nickel(II) complex; Synthesis; Crystal structure;

Two Mn(II)–Au(I) supramolecular assemblies bonded by coordination, aurophilicity and hydrogen-bonding, π–π interactions and their magnetic properties by Wen Dong; Yan Ouyang; Li-Na Zhu; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan; Peng Cheng (779-783).
Two Mn(II)–Au(I) supramolecular assemblies have been synthesized and structurally characterized by single crystal X-ray diffraction. The interplay of aurophilicity, coordination, hydrogen-bonding and π–π interactions in 1 and 2 result in three-dimensional network.Two Mn(II)–Au(I) supramolecular assemblies {{Mn[Au(CN)2]2(H2O)4} [Au(CN)2]2(H2bpy) · H2O}(bpy = 4,4′-bipyridine) 1 and {Mn(4,4′-dmbpy) [Au(CN)2]2(CH3OH)} (4,4′-dmbpy = 4,4′-dimethyl-bipyridine) 2 have been synthesized and magnetic properties have been investigated The interplay of aurophilicity, coordination, hydrogen-bonding and π–π interactions in two complexes result in three-dimensional network.
Keywords: Aurophilicity; Hydrogen-bonding; Magnetic properties; Three-dimensional network;

The complex Ag(NH3)NO2, which can be viewed as a ligand-based mixed-valence compound undergoes a photoconproportionation of nitrogen from −III and +III to 0. It is suggested that this photolysis originates from a NH3 to NO 2 - LLCT state which is populated from a NO 2 - IL state. In this context, the excited state properties of AgNO2 and Ag(H2O)NO2 are also discussed.The complex Ag(NH3)NO2, which can be viewed as a ligand-based mixed-valence compound, undergoes a photoconproportionation of nitrogen from −III and +III to 0. It is suggested that this photolysis originates from a NH3 to NO 2 - LLCT state which is populated from a NO 2 - IL state. In this context, the excited state properties of AgNO2 and Ag(H2O)NO2 are also discussed.
Keywords: Electronic spectra; LLCT; Nitrite complexes; Silver complexes; Photochemistry;

A unique 3-D 3d–4f heterometallic coordination polymer with double betaine ligand: Crystal structure and magnetic properties by Yan Li; Fa-Kun Zheng; Jian-Ping Zou; Wen-Qiang Zou; Hong-Wei Ma; Guo-Cong Guo; Can-Zhong Lu; Jin-Shun Huang (787-791).
A unique example of 3d–4f heterometallic coordination polymer with double betaine ligand, [GdCu2(L1)4(H2O)2](ClO4)7  · 6H2O 1 (L1  = 1,3-bis(pyridinio-4-carboxylato)-propane), has been synthesized and structurally charaterized. The structure of 1 contains an interesting 3-D NaCl-like framework with a 41263 topology constructed by the cross-linkage of the vertex-sharing double-paddle-wheel-like trinuclear [Cu(COO)4Gd(COO)4Cu] units and L1 ligands. No magnetic interaction between the Cu(II) and Gd(III) ions has been observed.A unique 3d–4f heterometallic coordination polymer with double betaine ligand, [GdCu2(L1)4(H2O)2](ClO4)7  · 6H2O 1 (L1  = 1,3-bis(pyridinio-4-carboxylato)-propane), has been synthesized by the self-assembly of Cu(ClO4)2 and Gd(ClO4)3 with flexible double betaine ligand L1, and structurally characterized by single-crystal X-ray diffraction. The structure of 1 can be regarded as being constructed by the cross-linkage of the vertex-sharing double-paddle-wheel-like trinuclear [Cu(COO)4Gd(COO)4Cu] units and L1 ligands to produce an interesting cationic NaCl-like framework with a 41263 topology, which is counter-balanced by the perchlorate ions located in the interspaces of the framework. Variable-temperature magnetic susceptibilities of 1 show there is no magnetic interaction between the Cu(II) and Gd(III) ions.
Keywords: Coordination polymer; Carboxylate ligands; Heterometallic complexes; Magnetic properties;

Stable complexes Cp 2 ∗ Ti ( η 2 -RCCR ) (R = Ph (2), Et (7)) were obtained in high yield by the reduction of Cp 2 ∗ TiCl 2 with magnesium in the presence of the corresponding alkyne, whereas the structure of Cp 2 ∗ Ti ( PhC CPh ) (2) was confirmed by X-ray studies for the first time.Stable complexes Cp 2 ∗ Ti ( η 2 -RCCR ) (R = Ph (2), Et (7)) were obtained in high yield by the reduction of Cp 2 ∗ TiCl 2 with magnesium in the presence of the corresponding alkyne, whereas the structure of Cp 2 ∗ Ti ( PhC CPh ) (2) was confirmed by X-ray studies for the first time.
Keywords: Titanocene; Diphenylacetylene; X-ray crystal structure;

Supramolecular assemblages from uranyl complexes of calixarenes and potassium complexes of 18-crown-6 or dibenzo-18-crown-6 by Pierre Thuéry; Bernardo Masci; Masashi Takimoto; Takehiko Yamato (795-799).
Two assemblages comprising uranyl/calixarene and potassium/crown ether complexes are described. A sandwich architecture is obtained with the smaller, cone-shaped p-tert-butyl[3.1.3.1]homocalixarene, whereas a columnar stacking is obtained with the larger and flatter p-tert-butylcalix[8]arene.Reaction of uranyl nitrate with p-tert-butyl[3.1.3.1]homocalixarene (L1H4) or p-tert-butylcalix[8]arene (L2H8) has been carried out in the presence of KOH and 18-crown-6 (18C6) or dibenzo-18-crown-6 (db18C6), giving the supramolecular assemblages [K(db18C6)(H2O)2]3 [{UO2(L1)}2K(H2O)5] (1) and [K(18C6)(OH)2][{(UO2)2(L2H5)(OH)}{K(18C6)}] (2). Compound 1 comprises a sandwich, “complex-within-complex” assemblage in which two uranyl/calixarene complexes encompass a potassium/crown ether guest. A direct bond between uranyl and K(18C6) is present in 2, in which a columnar arrangement of alternate dimetallic calixarene complexes and potassium/crown ether species is formed.
Keywords: Uranyl ion; Calixarenes; Homocalixarenes; Crown ethers; Supramolecular assemblage;

The benzoate/nitrate/2,2′:6′,2″-terpyridine ‘blend’ in lanthanide(III) chemistry: Relevance to the separation of lanthanides and actinides by solvent extraction by Argyro Messimeri; Christos Papadimitriou; Catherine P. Raptopoulou; Albert Escuer; Spyros P. Perlepes; Athanassios K. Boudalis (800-804).
An interesting dinuclear praseodymium(III) complex has been isolated from the PrIII/benzoate/nitrate/2,2′:6′,2″-terpyridine (▪) reaction system; omission of nitrates from the reaction mixture has resulted in a structurally similar complex.In an effort to better understand the nature of the species which may be involved in the selective extraction of actinides over the lanthanides – relevant to nuclear reprocessing – by 2,2′:6′,2″-terpyridine (terpy)-type ligands, in synergistic combination with a liphophilic carboxylic acid coextractant, the Pr III / PhCO 2 - / NO 3 - / terpy reaction system has been investigated. The investigation resulted in the isolation of the dinuclear complex [Pr2(O2CPh)5(NO3)(terpy)2(H2O)(MeOH)] (1), in which the metal ions are bridged by two η112 benzoate ligands. Omission of nitrates from the reaction mixture gives the structurally similar complex [Pr2(O2CPh)6(terpy)2(H2O)2] (2). IR and solid-state electronic spectra are discussed in terms of the nature of bonding and the known structures. No magnetic interaction was found between the PrIII ions in 2. The possible role of the carboxylic acid coextractant in the extraction process is discussed.
Keywords: Actinide–lanthanide separation; Magnetic properties; Nuclear reprocessing; Praseodymium(III) benzoate complexes; Praseodymium(III) nitrate complexes; Praseodymium/2,2′:6′,2″-terpyridine complexes;

A self-assembled pentanuclear single-stranded helicate based on the square-planar coordination geometries by Huan Liu; Hong Zhou; Zhi-Quan Pan; Dan Hu; Qi-Mao Huang; Han-Ping Zhang; Xue-Lei Hu; Xiang-Gao Meng (805-807).
The copper(II) complex of a new bis-N4O-hexdentate Schiff-base, in which two N,N′-dimethyl-N-(3-(2′- aminoethylimine)-5-(chlorosalicylamine))-N′-(3-imine-5-chlorosalicylamine) units are connected by an ethylene, was structurally characterized in the solid state as a pentanuclear single helicate based on the square-planar coordination geometries.The copper(II) complex of a new bis-N4O-hexdentate Schiff-base, in which two N,N′-dimethyl-N-(3-(2′-aminoethylimine)-5-(chlorosalicylamine))-N′-(3-imine-5-chlorosalicylamine) units are connected by an ethylene, was synthesized and structurally characterized in the solid state as a form of pentanuclear single helicate based on the square-planar coordination geometries.
Keywords: Single helicate; Copper(II) pentanuclear complex; Self-assembly; N4O ligands;

Intercalation of cation guests into a three-dimensional anionic host framework by Jian-Kai Cheng; Pei-Xiu Yin; Zhao-Ji Li; Ye-Yan Qin; Yuan-Gen Yao (808-810).
A new Cu(I) complex, { [ Cu ( dmp ) 2 + ] · [ 1 / 2 ( H 2 bdc ) · 1 / 2 ( bdc 2 - ) · 2 H 2 O ] } n (1) (dmp = 2,9-dimethyl-1,10-phenanthroline, bdc = 1,4-benzene-dicarboxylate), has been hydrothermally synthesized. It features a three-dimensional supramolecular host architecture with photosensitizer-dye cation guests, and all copper atoms are Cu+ and redox reaction occurred under the present hydrothermal condition.A new three-dimensional photoluminescent host–guest open-framework, { [ Cu ( dmp ) 2 + ] · [ 1 / 2 ( H 2 bdc ) · 1 / 2 ( bdc 2 - ) · 2 H 2 O ] } n (1) (dmp = 2,9-dimethyl-1,10-phenanthroline, bdc = 1,4-benzene-dicarboxylate), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectrum, fluorescent spectrum, and thermogravimetric analyses. The structure of complex 1 features a three-dimensional supramolecular host architecture with photosensitizer-dye cation guests. Although Cu2+ was used as the starting material, no obvious signal was observed in ESR spectrum of 1, which indicates that all copper atoms in 1 are Cu+ and redox reaction occurred under the present hydrothermal condition.
Keywords: Supramolecular; Host framework; Photo-luminescence; Hydrothermal reaction;

Twisted Pd(II) dinuclear complex, [Pd2(PMCB2−)Cl2], possesses extensive π–π interactions and C–H⋯O hydrogen bonding interactions between the Pd(II) dimers that gives rise to a 3D supramolecular network structure.Dinuclear Pd(II) compound, [Pd2(PMCB2−)Cl2] · CH2Cl2 (1), has been prepared by the reaction of K2[PdCl4] with exo-hexadentate ligand having amide groups (3,3′-bis[N-(2-pyridylmethyl)carbamoly]-2,2′-bipyridine, H2PMCB) in H2O/CH2Cl2. X-ray crystal structure of 1 indicates that one PMCB2− ligand binds two Pd(II) ions each having a distorted square planar structure. The bipyridine group of the PMCB2− ligand is involved in offset face-to-face π–π interactions, which gives rise to a 1D chain. The 1D chains are linked together via the C–H⋯O hydrogen bondings between a carbon atom of pyridine group and the oxygen of carbamoly group to generate a 2D network. Between the 2D networks there exist the herringbone π–π stackings, which results in a 3D supramolecular structure.
Keywords: Exo-hexadentate ligand; Dinuclear palladium(II) complex; Crystal structure; Hydrogen bonding; Offset π–π interaction;

A 2D coordination polymer with brick-wall network topology based on the [Cu(NCS)2(pn)] monomer by A.O. Legendre; A.E. Mauro; J.G. Ferreira; S.R. Ananias; R.H.A. Santos; Adelino V.G. Netto (815-820).
The complex [Cu(NCS)2(pn)] self-assembles into a 2D metal-organic framework with a brick-wall network topology via μ-1,3,3-thiocyanato bridges and hydrogen bonding.The new complex [Cu(NCS)2(pn)] (1) (pn = 1,3-propanediamine) has been synthesized and characterized by elemental analysis, infrared and electronic spectroscopy. Single crystal X-ray diffraction studies revealed that complex 1 is made up of neutral [Cu(NCS)2(pn)] units which are connected by μ-1,3,3-thiocyanato groups to yield a 2D metal-organic framework with a brick-wall network topology. Intermolecular hydrogen bonds of the type NH⋯SCN and NH⋯NCS are also responsible for the stabilization of the crystal structure.
Keywords: Supramolecular chemistry; Self-assembly; Copper(II); Coordination polymer; Hydrogen bonding;

Synthesis, characterization, and fluorescence and cytotoxicity studies of a tetrarhenium molecular rectangle by Dejene K. Orsa; Gregory K. Haynes; Saroj K. Pramanik; Maurice O. Iwunze; George E. Greco; Jeanette A. Krause; Douglas M. Ho; Arthur L. Williams; Dwayne A. Hill; Santosh K. Mandal (821-824).
The molecular rectangle [(CO)3Re(μ-OC5H11)2Re(CO)3]2{μ-(4,4′-bpy)}2 (I), which is cytotoxic against cancer cells, has been synthesized in high yield from one-pot reaction of Re2(CO)10 with 4,4′-bpy in refluxed 1-pentanol.An one-pot reaction of Re2(CO)10 with 4,4′-bipyridyl (4,4′-bpy) in refluxed 1-pentanol afforded the molecular rectangle, [(CO)3Re(μ-OC5H11)2Re(CO)3]2{μ-(4,4′-bpy)}2 (I), in almost quantitative yield. The molecular rectangle, I, has been characterized spectroscopically and by X-ray crystal structure determination. Compound I exhibits fluorescence and is cytotoxic against cancer cell lines.
Keywords: Rhenium; Molecular rectangle; Crystal structure; Fluorescence; Cancer cell lines;

Cyclopalladated hydrazones complexed to pyridinyl ligands by Iolinda Aiello; Mauro Ghedini; Massimo La Deda; Tonino Martino (825-828).
Two series of PVP polymers grafting various amount of Pd(II) complexes of terdentate hydrazones were successfully synthesized. The obtained products were characterized in solution and as spin coated thin films.2-Benzoylpyridine and 2-acetylpyridine N-methyl-N-phenylhydrazones (HL 1 and HL 2) in cyclopalladation reactions with Pd3(OAc)6 behave as N(py)N(im)C tridentate ligands and form the neutral mononuclear complexes [Pd(k 3-N,N,C–L1,2)(k 1-OAc)] (1 and 2). The labile OAc ligand can be replaced by pyridine (py) and, in the presence of NH4PF6, a compound of the general formula [Pd(k 3-N,N,C-L1,2)(py)]PF6 (3 and 4) can be obtained. Reacting 1 or 2 with the poly(4-vinylpyridine) polymer (PVP, M ¯ w = 160 000 ) adducts of the general formula x[Pd(k 3-N,N,C-L1,2)(PF6)] ·  y[PVP] gives (5ac and 6ac, ac: x/y  = 80/20, 50/50, 25/75 w/w) containing the laterally appended cyclopalladated “Pd(k 3-N,N,C-L1,2)” fragments. These metallorganic polymers show high glass transition temperatures, high thermal stability and good solubility, and are optimal for obtaining transparent thin films by the spin coating method.
Keywords: Phenylhydrazones; Tridentate ligands; Cyclometallation; Palladium compounds; Grafted polymers; Metal–polymer complexes;

The treatment of the (4-pyridylthio) acetic acid and lanthanide nitrates under hydrothermal conditions leads to generate the two-dimensional lanthanide coordination polymers involving in situ C–S bond cleavage and (4-pyridylthio) acetic acid was transformed into 4-pyridinethiolate and oxalate.Lanthanide coordination polymers with the formula [Ln2(C2O4)3(H2O)6] n (1) (Ln = Nd, 1) and [Ln2(C2O4)3(pythioH)2(H2O)2] n (Ln = Eu 2; Dy 3; Er 4) pythio = 4-pyridinethiolate) were synthesized by treating LnIII nitrates with (4-pyridylthio)acetic acid under hydrothermal conditions. Single-crystal X-ray diffraction studies indicate that these lanthanide coordination polymers consist of extended oxalate-bridged two-dimensional layer structure. Interestingly, in situ C–S bond cleavage occurred and (4-pyridylthio)acetic acid was transformed into 4-pyridinethiolate and oxalate. The complexes 2 and 3 display strong fluorescent emission in the solid state at room temperature.
Keywords: Synthesis; Crystal structure; Coordination polymers; Luminescent properties;

View of the 4 · 82 polyhedral network of ZnO3Cl and HPO3 tetrahedra.C5H14NO · ZnCl(HPO3) arose from an unexpected reaction in which a component of the ionic liquid mixed solvent was incorporated into a hybrid structure in which cholinium (C5H14NO+) cations interact with [ZnCl(HPO3)] macroanionic layers by way of O–H⋯O hydrogen bonds. The inorganic layers display a 4 · 82 topology.
Keywords: Hybrid solids; Ionic liquids; Zinc; Phosphorus;

The target compound was obtained through solvothermal reaction route, which exhibits a 3D layered network. This net represents a rare trinodal (42  · 84) (43  · 63)2 (46  · 63  · 86)2 topology.A new manganese polymer Mn3(ptc)2(H2O)4 (1) (H3ptc = Pyridine-2,4,6-tricarboxylic acid) has been solvothermally synthesized and characterized by single-crystal diffraction, IR, TGA and elemental analysis. Compound 1 crystallizes in the triclinic space group P 1 ¯ and shows a fairly complicated structure, which should be attributed to the high connectivity of H3ptc ligand. Meanwhile, we defined a novel trinodal (42  · 84)(43  · 63)2(46  · 63  · 86)2 topology net, two types of Mn(II) ions in different chemical environment and ptc3− anion act as four-connected, four-connected and six-connected node, respectively. The magnetic measurement in the temperature range of 2–300 K displays weak antiferromagnetic coupling interaction between the Mn(II) ions.
Keywords: Novel topology; Pyridine-2,4,6-tricarboxylate; Manganese(II); Magnetic behavior; Solvothermal synthesis;

A novel multichain polymer (bbi)1.5[Cu(bbi)]4.5[PW12O40]1.5 (1), based on flexible 1,1′-(1,4-butanediyl)bis(imidazole) (bbi) ligand and Keggin polyoxoanion, was synthesized under the hydrothermal conditions. Compound 1 features in two sorts of polyoxometalates (POMs) chains, the poly-chain of [Cu(bbi)]4.5[PW12O40] and the single-chain of (bbi)[PW12O40]0.5, induced by the POM clusters.By introducing the flexible 1,1′-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the Keggin system, a novel multi-chain compound, (bbi)1.5[Cu(bbi)]4.5[PW12O40]1.5 (1) was synthesized under the hydrothermal conditions. It was characterized by elemental and TG analysis, IR and XPS spectra, cyclic voltammetry, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Compound 1 features in two sorts of polyoxometalates (POMs) chains, the poly-chain of [Cu(bbi)]4.5[PW12O40] and the single-chain of (bbi)[PW12O40]0.5, induced by the POM clusters.
Keywords: Hydrothermal synthesis; Keggin; Polyoxometalate; Flexible ligand;

Copper(II) azide complexes of [Cu(acac)(N3)(dpyam)] and [Cu(μ-N3N1)(C2N3N1)(dpyam)]2: Synthesis, crystal structure and magnetism by Sujittra Youngme; Thidarat Chotkhun; Narongsak Chaichit; Gerard A. van Albada; Jan Reedijk (843-848).
Two new compounds, [Cu(acac)(N3)(dpyam)] (1), (acac = acetylacetonate; dpyam = di-2-pyridylamine) and [Cu(μ1,1-N3)(C2N3)(dpyam)]2 (2), have been synthesized and characterized by single-crystal X-ray diffraction and magnetic analyses. Compound 1 is a mononuclear compound in which each of two independent Cu(II) ions is penta-coordinated with a distorted square pyramidal geometry with distortion parameters τ  = 0.21 and 0.16. In contrast, compound 2 is an azido-bridged dinuclear compound with monodentate dicyanamide anions and the Cu(II) ions display a distorted trigonal bipyramidal geometry with τ  = 0.73 and end-on azido bridges providing an equatorial–axial position between the metal ions. Magnetic susceptibility measurements of compound 2 reveal a very weak ferromagnetic interaction between the Cu(II) ions with a J value of +5.8 cm−1.Two new compounds, [Cu(acac)(N3)(dpyam)] (1), (acac = acetylacetonate; dpyam = di-2-pyridylamine) and [Cu(μ-N3N1)(C2N3- κN1) (dpyam)]2 (2), have been synthesized and characterized by single-crystal X-ray diffraction and magnetic analyses. Compound 1 is a mononuclear compound in which each of two independent Cu(II) ions is penta-coordinated with a distorted square pyramidal geometry with distortion parameters τ  = 0.21 and 0.16. In contrast, compound 2 is an azido-bridged dinuclear compound with monodentate dicyanamide anions and the Cu(II) ions display a distorted trigonal bipyramidal geometry with τ  = 0.73 and end-on azido bridges providing an equatorial–axial position between the metal ions. The EPR spectra of powdered samples for 1 and 2 have also been investigated. Magnetic susceptibility measurements of compound 2 reveal a very weak ferromagnetic interaction between the Cu(II) ions with a J value of +5.8 cm−1.
Keywords: Copper(II); Crystal structure; Magnetism; Di-2-pyridylamine; Azide bridges; Dicyanamide;

The title compound [Co(en)2(H2O)]{[Co(en)2]2As8V14O42(SO4)} · 3H2O (1) (en = ethylenediamine) has been hydrothermally synthesized. The single crystal diffraction analysis shows that compound 1 exhibits {[Co(en)2]2As8V14O42(SO4)}n 2n layers act as ligand of coordination cations [Co(en)2]2+, and water molecules are inserted in the layers.The title compound [Co(en)2(H2O)]{[Co(en)2]2As8V14O42(SO4)} · 3H2O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum and thermogravimetric analysis. The single crystal diffraction analysis shows that compound 1 exhibits {[Co(en)2]2As8V14O42(SO4)}n 2n layers act as ligand of coordination cations [Co(en)2]2+, and water molecules are inserted in the layers. The magnetic measurement indicates a weak antiferromagnetic exchange coupling within the molecular unit, which is deemed to attribute to the contribution of Viv and Co2+.
Keywords: Arsenic–vanadate; Cluster; Hydrothermal synthesis; Crystal structure;