Inorganic Chemistry Communications (v.14, #6)

Contents List (iii-xix).

An unusual 3D pillared-layer cobalt(II) coordination polymer containing helical motifs and novel topology constructed from mixed ligands by Guo-Ping Yang; Bin Liu; Lei Hou; Ping Liu; Bo Liu; Yao-Yu Wang; Qi-Zhen Shi (805-808).
An unusual 3D pillared-layer CoII coordination polymer, namely [Co(pda)(bpe)] n (1) [H2pda = 1,3-phenylenediacetic acid, bpe = 1,2-bi(4-pyridyl)ethylene], has been successfully prepared under hydrothermal condition. X-ray crystal analysis indicates that the structure of 1 is constructed from 2D undulated [Co(pda)] n layers, which consists of alternating left- and right-handed helical motifs, and then further pillared by bpe ligands into a 3D structural framework. Topologically, complex 1 shows an intriguing binodal (3,5)-connected fsc network with the Schläfli symbol of (4.62)(4.66.83) which is completely different from the reported (4,6)-connected fsc nets; and if the dimeric [Co2] units (SBUs) are considered as the single 6-connected nodes, 1 displays a familiar uninodal pcu net with the Schläfli symbol of (412.63). In addition, magnetic measurement revealed that 1 shows the antiferromagnetic coupling between CoII ions.An unusual 3D pillared-layer CoII coordination polymer, namely [Co(pda)(bpe)]n (1), has been successfully prepared under hydrothermal condition. X-ray crystal analysis indicates that the structure of 1 is constructed from 2D undulated [Co(pda)]n layers, which consists of alternating left- and right-handed helical motifs, and then further pillared by bpe ligands into a 3D framework. Topologically, 1 shows an intriguing binodal (3,5)-connected fsc network with the Schläfli symbol of (4.62)(4.66.83); and if the dimeric [Co2] units are considered as the single 6-connected nodes, 1 displays a familiar pcu net with the Schläfli symbol of (412.63). The magnetic measurement revealed that 1 shows the antiferromagnetic coupling between the CoII ions.Display Omitted► The 2D undulated layer of 1 consists of alternating left- and right-handed helical motifs. ► The overall structure of 1 shows an intriguing 3D binodal (3,5)-connected fsc network. ► Complex 1 displays a familiar uninodal pcu net based on the dimeric [Co2] units (SBUs). ► The magnetic measurement revealed that 1 shows the antiferromagnetic coupling between CoII ions.
Keywords: Coordination polymer; Cobalt(II); Topology; Helical motif; Magnetic property;

The new nickel bis(dithiolene) complex [Bu4N]2[Ni(6,7-qdt)2] (1) (6,7-qdt = quinoxaline-6,7-dithiolate) has been synthesized, starting from quinoxaline-6,7-dithiol, nickel chloride and tetrabutylammonium bromide in methanol. Compound 1 crystallizes in P2 1 /c space group (monoclinic system). Its crystal structure has been characterized by interesting C―H⋅⋅⋅S and C―H⋅⋅⋅N weak interactions resulting in a three dimensional supramolecular network. Complex 1 shows solvent sensitive absorption band (broad feature) in the visible region, which is attributed to charge transfer (CT) transition involving electronic excitation from a HOMO that is a mixture of dithiolate (π) and metal (d) orbital character to a LUMO which is a π* orbital of the dithiolate. This CT transition absorbs at low energy region in comparison to the CT band of the [Bu4N]2[Ni(qdt)2] in the visible region. Interestingly, compound 1 undergoes reversible oxidation at very low oxidation potential (E 1/2  = + 0.12 V vs Ag/AgCl) compared to that of [Ni(qdt)2]2− (E 1/2  = + 0.41 V vs Ag/AgCl) in MeOH solutions.A new nickel-bis(dithiolene) complex [Bu4N]2[Ni(6,7-qdt)2] (1) (6,7-qdt = quinoxaline-6,7-dithiolate) has been synthesized and characterized. Its electronic absorption and electrochemical properties are discussed in comparison with those of [Bu4N]2[Ni(qdt)2] complex.Display Omitted► A new nickel bis(dithiolene) complex has been synthesized based on quinoxaline-6,7-dithiolate. ► Its crystal structure has been characterized by C–H···S and C–H···N weak interactions. ► The title compound undergoes reversible oxidation at a very low oxidation potential.
Keywords: Nickel(II)-dithiolene; Crystal structure; Supramolecular chemistry; Electronic absorption; Electrochemistry;

Molecular self-assembly of cadmium-triazolate complexes via hydrogen bonding: Synthesis, structures and photoluminescent properties by Kafeel Ahmad Siddiqui; Gopal K. Mehrotra; S.S. Narvi; Raymond J. Butcher (814-817).
Two new cadmium coordination polymers namely [Cd(HAmTrz–COO)4(NH4 +)2] 1; and [Cd(HAmTrz)2I2]n 2; (HAmTrz–COOH = 3-amino-1,2,4-triazole-5-carboxylic acid), have been prepared based on HAmTrz–COOH as ligand. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction technique. In coordination-complex 1 four triazole ligands coordinate via N1 nitrogen leading to a tetrahedral geometry around cadmium ion, while in 2 the ligand prefers to coordinate to the metal in a bidentate bridging mode. The structures of both the coordination polymers can be envisaged as 3D hydrogen bonded networks. Thermogravimetric analysis shows that 2 is more stable than 1 owing to different coordination numbers of cadmium atoms. Photoluminescence properties of both the compounds have been investigated in the solid state.The synthesis of two new cadmium coordination polymers namely [Cd(HAmTrz–COO)4(NH4 +)2] 1; and [Cd(HAmTrz)2I2]n 2; (HAmTrz–COOH = 3-amino-1,2,4-triazole-5-carboxylic acid) have been accomplished via variations in the reaction conditions. Both the compounds self-assemble into 3D hydrogen bonded networks assisted by supramolecular synthons. Thermal and photoluminescence properties have been examined in the solid state.Display Omitted► In both the polymeric structures, hydrogen bonds working in cooperativity with covalent interactions are capable of ‘maneuvering’ complex ions into desirable motifs. ► These are one of a few d10 transition metal coordination polymers where phenomenon of cooperativity of hydrogen bonding is very prominently manifested in the robustness of the overall framework structures.
Keywords: Cadmium triazolate; Coordination polymers; Homo and heteromeric H-bonding synthons;

Two new 2D coordination polymers containing bowl-shaped voids assembled from the bis(chelating) bridging ligand by Sheng-Run Zheng; Song-Liang Cai; Jun Fan; Tian-tian Xiao; Wei-Guang Zhang (818-821).
Two new coordination polymers, {[Mn3(BIC)3(H2O)4]∙C2H5OH∙H2O}n (1) and {[Mn3(BIC)3(H2O)4]∙C3H6O∙H2O}n (2, C3H6O = acetone), were obtained under hydrothermal conditions. Both of them are 2D networks containing bowl-shaped voids, which are occupied by EtOH and Me2CO molecules, respectively. Furthermore, the single 2D layer is chiral, which is assembled by the bis(chelating) bridging ligands and two kinds of Mn(II) coordination units.Two 2D Mn(II) coordination polymers containing bowl-shaped voids and containing homochiral layer assembled from the bis(chelating) bridging ligand and two kinds of Mn(II) units.Display Omitted► They are first 2D coordination polymers based on bisdidentate BIC2− ligands. ► Coordination polymers containing neutral homochiral honeycomb layers. ► Coordination polymers containing bowl-shaped neutral space.
Keywords: Coordination polymer; Bis(chelating) bridging ligand; Bowl-shaped voids;

Two new self-penetrating metal-organic frameworks based on a flexible cyclohexanetetracarboxylate ligand by Bo Liu; Lei Hou; Yao-Yu Wang; Ya-Nan Zhang; Lin Cui; Qi-Zhen Shi (822-825).
Two new metal-organic frameworks, [M2(CTA)(bipy)1.5(H2O)2] n ·3n(H2O) (M = Cd for 1 and Mn for 2, H4CTA = cyclohexane-1,2,4,5-tetracarboxylic acid, bipy = 4,4′-bipyridine) have been successfully synthesized and characterized. Complexes 1 and 2 are isostructural, which display unusual three-dimensional (3D) self-penetrating coordination frameworks with 3-nodal (3,5,5)-connectivity and the Schläfli symbol of (4,6,8)(42,67,8)(43,63,83,9). Moreover, in solid state, complex 1 exhibits blue emission at ambient temperature. Magnetic measurement shows that there exist weak antiferromagnetic interactions in 2.Two new isostructural 3D self-penetrating metal-organic frameworks [M2(CTA)(bipy)1.5(H2O)2] n ·3n(H2O) (M = Cd for 1 and Mn for 2) have been successfully synthesized and characterized. They represent the first example that using conformation flexible cyclohexane-carboxylic acid as linking ligand to construct self-penetration framework.Display Omitted► Two new isostructural 3D self-penetrating metal-organic frameworks. ► The first cyclohexane-carboxylic self-penetration framework. ► In solid state, complex 1 exhibits blue emission, and 2 shows antiferromagnetic.
Keywords: Metal-organic framework; Self-penetrating; Luminescence; Magnetic property;

Two novel porous luminescent lanthanide-organic frameworks with new four-nodal (3,4)-connected network topology by Sheng-Run Zheng; Song-Liang Cai; Qing-Yuan Yang; Tian-Tian Xiao; Jun Fan; Wei-Guang Zhang (826-830).
Two new porous lanthanide-organic frameworks, {[Ln2(HIDC)3(H2O)2]·7H2O}n [Ln = Tb(1) and Eu(2), H3IDC = imidazole-4,5-dicarboxylic acid], were obtained under hydrothermal conditions. Both of them possess 3D frameworks containing 1D rectangle channels along a-axis. Topological analyses of two complexes reveal that they exhibit unusual 4-nodal (3,4)-connected network. Furthermore, their solid-state luminescent behaviors have been investigated at room temperature.Two 3D porous lanthanide-organic frameworks containing 1D rectangle channels along a direction feature unusual 4-nodal (3,4)-connected network topology as well as show strong fluorescent emission.Display Omitted► Two 3D porous frameworks constructed by H3IDC ligand and lanthanides ions. ► Frameworks containing 1D rectangle channels. ► Frameworks with novel four-nodal (3,4)-connected network topology.
Keywords: Porous lanthanide-organic framework; Imidazole-4,5-dicarboxylic acid; (3,4)-connected network topology; Luminescence;

Synthesis and photophysical studies of two luminescent chemosensors based on catechol and 8-Hydroxyquinoline chromophores, and their complexes with group 13 metal ions by Cristina Nuñez; Javier Fernandez-Lodeiro; Mário Dinis; Miguel Larguinho; José Luis Capelo; Carlos Lodeiro (831-835).
Two ligands, L1 and L2, derived from 2,3-dihydroxybenzaldehyde and 8-hydroxyquinoline-2-carbaldehyde using 4,4′-methylene-dianiline as spacer have been used to study their interaction with the group 13 metals, Al3+, Ga3+ and In3+. In all cases, emissive dinuclear metal complexes were synthesized and characterized. The complexation reactions with the diiminic ligands were obtained by direct reactions between ligand and metal ions. The complexes have been characterized by elemental analyses, mass spectrometry, IR, UV–vis and fluorescence spectroscopy. The interaction towards metal ions has been explored in solution by absorption and fluorescence emission spectroscopy, obtaining results that support the solid-state helicate-type complexes.Two ligands, L1 and L2, derived from 2,3-dihydroxybenzaldehyde and 8-hydroxyquinoline-2-carbaldehyde using 4,4′-methylene-dianiline as spacer have been used for the interaction with the group 13 metals, Al3+, Ga3+ and In3+. In all cases, emissive dinuclear metal complexes were synthesized and characterized.Display Omitted► New emissive Helicate complexes derived of the group 13 metals, Al3+, Ga3+ and In3+.
Keywords: Aluminum; Galium; Indium; Complexes Schiff-base helicates;

Shifts of Ni(II)/Ni(III) redox potentials of a nickel-pincer complex, [Ni(SCS)Br] (SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl), on addition of bases have been investigated. The complex showed two-step shifts of the Ni(II)/Ni(III) redox potential, and the shifts are associated to two-step deprotonation of the SCS ligand on addition of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). DBU led to a negative shift of the Ni(II)/Ni(III) redox potential by approximately 500 mV.A nickel-pincer complex, [Ni(SCS)Br] (SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl) showed a two-step deprotonation reaction by treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The addition of DBU led to a negative shift of Ni(II)/Ni(III) redox potential by ca. 500 mV.Display Omitted► Addition of bases to an Ni-(SCS) pincer complex shifts the redox potential to lower. ► DBU led to a negative shift of the redox potential of the complex by ca. 500 mV. ► A first redox potential-controllable Ni-(SCS) pincer complex by pH was developed.
Keywords: Nickel; Pincer complex; Secondary thioamide; Electrochemistry; UV–vis spectra; Acid–base equilibrium;

A Fe17 cluster with S = 35/2 ground state: Synthesis, structure, and magnetic properties by Zhi-Guo Gu; Bao-Xiang Wang; Jing-Jing Na; Xin-Hui Zhou; Zaijun Li (839-842).
A new polyiron complex [Fe17(OH)7O11(O2CPh)20(N3)2]·4H2O·10MeCN (1), with compact [Fe17(OH)7O11] core encapsulated by twenty benzoate anions and two end-on (EO) azido ligands has been synthesized and structurally characterized. Intramolecular antiferromagnetic couplings are observed for 1 and it has S = 35/2 ground state which was confirmed by magnetic measurements and Mössbauer spectra.A novel polyiron cluster [Fe17(OH)7O11(O2CPh)20(N3)2]·4H2O·10MeCN (1) has been synthesized and structurally characterized. Magnetic measurements and Mössbauer spectra studies indicate that cluster 1 has S = 35/2 ground state.Display Omitted► Fe17 cluster contains both oxo and end-on azido bridges. ► Seventeen iron(III) ions are encapsulated by twenty benzoate and two azido ligands. ► Fe17 cluster has large ground spin state of S = 35/2.
Keywords: Iron(III); Oxo/azido-bridged cluster; Self-assembly; Benzoate ligand;

Synthesis, structures and luminescent properties of Ca(II), Sr(II) and Pb(II) coordination compounds based on new flexible ligand 5-(2-pyrazinyl)tetrazole-2-acetic acid by Qiao-Yun Li; Feng Zhou; Chun Zhai; Lei Shen; Xiao-Yan Tang; Jie Yang; Gao-Wen Yang; Zhu-Feng Miao; Jian-Ning Jin; Wei Shen (843-847).
Reactions of Hpztza (Hpztza = 5-(2-pyrazinyl)tetrazole-2-acetic acid) with CaCl2 , SrCl2 or Pb(NO3)2 with the presence of KOH under hydrothermal condition, produced three new coordination compounds, [M(pztza) 2(H2O)2][M = Ca (1), M = Sr (2)] and [Pb(pztza)2]·H2O (3). These compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compounds 12 display zigzag chain structure while 3 features a linear chain structure. Furthermore, the luminescence properties of 13 were investigated at room temperature in the solid state. The photoluminescent mechanism of 13 is tentatively attributed to an intraligand emission state.Display Omitted► Reactions of Hpztza (Hpztza = 5-(2-pyrazinyl)tetrazole-2-acetic acid) with CaCl2, SrCl2 or Pb(NO3)2 under hydrothermal conditions, produced three new coordination compounds, [M(pztza) 2(H2O)2][M=Ca(1), M=Sr(2)]and [Pb(pztza)2]·H2O (3). ► These compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. ► Compounds 13 display 1D structures. ► Furthermore, the luminescence properties of 13 were investigated at room temperature in the solid state.
Keywords: Ca(II); Sr(II); Pb(II); 5-(2-pyrazinyl)tetrazole-2-acetic acid; Crystal structure; Luminescence;

A novel 3D cadmium coordination polymer constructed from hydrazine and benzene-1,2,4,5-tetracarboxylic acid: Synthesis, structure and fluorescent property by Xiao-Yang Yu; Xiao-Bing Cui; Xiao Zhang; Li Jin; Ya-Nan Luo; Jia-Jun Yang; Hong Zhang; Xiang Zhao (848-851).
A novel three-dimensional (3D) coordination polymer [Cd(bta)0.5(N2H4)(H2O)]·H2O (1) (H4bta = benzene-1,2,4,5-tetracarboxylic acid; N2H4  = hydrazine) was synthesized hydrothermally and characterized by IR, elemental analysis, TGA and X-ray diffraction analysis. Compound 1 is the first example of 3D coordination compound containing trans-μ 2-bridging ligand N2H4. In 1, Cadmium atoms are coordinated by bta4− ligands to form sinusoidal ruffling layers and the layer are further linked by hydrazine ligands into 3D network with a (83)(85·10) topology structure. In addition, the thermogravimetric analysis and fluorescent property of compound 1 have been investigated.A novel 3-D cadmium coordination compound was synthesized through hydrothermal reaction between cadmium salt and H4bta and N2H4·H2O. Hydrazine ligands and bta4− ligands are connected by Cd cations into simultaneously single-left and single-right-helice channels. Compound 1 would be an excellent candidate as light-emitter applications owing to its strong fluorescence emission.Display Omitted► 1 is the first example that N2H4 ligands act as bridging ligands in the 3D network. ► H4bta is very popular to build coordination polymers with fascinating architectures. ► 1 would be an excellent candidate as light-emitter applications.
Keywords: Crystal structure; Hydrazine; Benzene-1,2,4,5-tetracarboxylate; Coordination polymer; Photoluminescence property;

pH-induced fluorescence switch of two novel tetranuclear Ru(II) polypyridyl complexes by Feixiang Cheng; Ning Tang; Jishu Chen; Fan Wang; Longhai Chen (852-855).
Tetrapodal ligands tetrakis{4-((1,10-phenanthroline-[5,6-d]imidazol-2-yl)phenoxy)methyl}methane (L1), tetrakis{3-((1,10-phenanthroline-[5,6-d]imidazol-2-yl)phenoxy)methyl}methane (L2), and corresponding Ru(II) complexes [(bpy)8L1–2(RuII)4](PF6)8, shortly called Ru–L1–2, have been synthesized and characterized. The pH effects on UV–vis absorption and fluorescence spectra of the two complexes are studied, and ground- and excited-state ionization constants of the two complexes are derived. The two complexes act as pH-induced “off–on–off” fluorescence switches through protonation and deprotonation in buffer solution at room temperature.Two novel tetranuclear Ru(II) complexes with imidazole rings uncoordinated to the metal ion center have been prepared. The two complexes behave as pH-induced off–on–off fluorescence switches due to their interesting ptoton-dependent photophysical properties.Display Omitted► Synthesis two tetranuclear Ru(II) complexes with imidazole rings. ► The two complexes show interesting proton-dependent photophysical properties. ► The two complexes act as “off–on–off” fluorescence pH switches.
Keywords: Tetranuclear Ru(II) complex; pH switch; UV–vis absorption; Fluorescence;

3,4,10-trihydro-2H,6H-naphtho[1,8-cd][1,5]diselenacyclodecane, L, has been prepared by the reaction of NCSe(CH2)3SeCN and 1,8-bis-bromomethylnaphthalene. L and [Mo(CO)4 L] have been characterized by a range of analytical techniques.3,4,10-trihydro-2H,6H-naphtho[1,8-cd][1,5]diselenacyclodecane, L, has been prepared by an efficient route. The structures and spectral analysis of L and [Mo(CO)4 L] were studied.Display Omitted► A novel macrocyclic diselenoether based on naphathalene ring has been prepared. ► For the first time, the stable complex of this kind of ligands is isolated.
Keywords: 3,4,10-trihydro-2H,6H-naphtho[1,8-cd][1,5]diselenacyclodecane; Mo(0) tetracarbonyl complex; Crystal structure;

Two heterobimetallic complexes of [(TBBP)2Mg][(Na)2(THF)4] 1 [TTBP-H2  = 2,2′-dihydroxy-3,3′,5,5′-tetra-tert-butyl-1,1′-diphenyl] and [(TBBP)2Mg][(Li)2(THF)4] 2 can initiate the ring-opening polymerization of l-lactide. And the experiment results show that complex 1 can initiate the ring-opening polymerization of l-lactide under an air atmosphere with high conversion, indicated that 1 is a robust catalyst in the polymerization of l-LA.Two heterobimetallic complexes of [(TBBP)2Mg][(Na)2(THF)4] 1 and [(TBBP)2Mg][(Li)2(THF)4] 2 can initiate the ring-opening polymerization of l-lactide. And complex 1 can initiate the ring-opening polymerization of l-lactide in an open atmosphere with high conversion.Display Omitted► Hetero-bimetallic complexes of 12 were prepared in an analogous manner. ► Fine crystals 1 and 2 were obtained by crystallization from THF and toluene. ► Complexes of 12 were used as catalyst in the polymerization of L-LA. ► Complex 1 can initiate polymerization of L-LA exposed to air with high conversion.
Keywords: Heterobimetallic complexes; l-lactide; Robust catalyst; Ring-opening polymerization;

Rapid and efficient oxidation of 2-substituted imidazolines with sodium periodate is reported. The Mn(III)–salophen/NaIO4 catalytic system efficiently converted 2-imidazolines to their corresponding imidazoles at room temperature in 2: 1, CH3CN/H2O mixture.Rapid and efficient oxidation of 2-substituted imidazolines with sodium periodate is reported. The Mn(III)-salophen/NaIO4 catalytic system efficiently converted 2-imidazolines to their corresponding imidazoles at room temperature in 2: 1, CH3CN/H2O mixture. The effect of reaction parameters such as kind of solvent and catalyst amount was also investigated.Display Omitted►Biomimetic oxidation of 2-imidazolines with NaIO4 catalyzed by Mn(salophen) ►The corresponding 2-imidazoles were obtained in excellent yields ►The reaction were less than 30 min.
Keywords: Imodazoline; Imidazole; Mn(III) salophen; Periodate; Biomimetic oxidation;

An unusual two-dimensional 2-fold interpenetrating metal-organic framework based on tetranuclear manganese(II) clusters: Synthesis, structure and magnetic properties by Guang-Xiang Liu; Xiao-Chun Cha; Xin-Long Li; Chun-You Zhang; Yan Wang; Sadafumi Nishihara; Xiao-Ming Ren (867-872).
A novel coordination polymer, [Mn2(DBA)2(bix)0.5] (1) (H2DBA = 4,4′-methylenedibenzoic acid, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), has been synthesized under hydrothermal condition, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. X-ray single-crystal structural analyses reveal that complex 1 exhibits a two-dimensional 2-fold interpenetrating (4,4) frameworks based on tetranuclear [Mn4(CO2)8] secondary building units, and further assembled into a three-dimensional supramolecular structure via π-π stacking interaction. Moreover, variable–temperature magnetic susceptibility studies indicate weak antiferromagnetic exchange interactions between the magnetic centers.A novel coordination polymer, [Mn2(DBA)2(bix)0.5], have been synthesized under hydrothermal conditions. The complex exhibits a two-dimensional interpenetrating (4, 4) frameworks based on tetranuclear [Mn4(CO2)8] secondary building units, and further assembled into a three-dimensional supramolecular structure via π-π stacking interaction. Variable–temperature magnetic susceptibility studies indicate weak antiferromagnetic exchange interactions.Display Omitted► Coordination polymer based on 4,4′-methylenedibenzoic acid is not reported so far. ► The first examples of two-dimensional 2-fold interpenetrating metal-organic framework based on tetranuclear manganese(II) clusters. ► Variable-temperature magnetic susceptibility studies indicate weak antiferromagnetic exchange interactions between the magnetic centers.
Keywords: Manganese(II) coordination polymer; Crystal structure; Tetranuclear; Magnetism;

Assemblies of 3,5-bis(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole (L 3 ) with Cd(II) in the presence of different pseudohalide anions [N3 , dca (dicyanamide) or SCN] produce three distinct coordination polymers, i.e. {[Cd5(L 3 )2(H2O)2(N3)10](CH3OH)2(H2O)4} n (1), [Cd(L 3 )2(dca)2] n (2) and [Cd(L 3 )2(SCN)2] n (3). In 1, the N3 anions with three different coordination modes bridge the Cd(II) ions to form 2-D inorganic layers, which are extended by the tridentate L 3 ligands to result in a 3-D coordination framework. In 2 and 3, the anion (dca or SCN) takes the terminal coordination and L 3 acts as the bidentate bridge, resulting in 1-D double-strand chain for 2 and double-strand chiral helix for 3. Thermal stability and fluorescence for 1–3 are also presented.This work presents the syntheses, structures, and properties of three Cd(II) coordination polymers with a tripyridyltriazole ligand, which exhibit distinct 3-D coordination network and 1-D double-strand chain or chiral helix arrays directed by the pseudohalide anions.Display Omitted► Three distinct Cd(II) coordination polymers are constructed based on a novel tripyridyltriazole tecton. ► Their polymeric structures are regulated by different pseudohalide anions. ► Solid state fluorescent emissions are available at room temperature.
Keywords: Cd(II) coordination polymers; Pseudohalide anions; Crystal structures; Tripyridyltriazole; Fluorescence;

A cubane-like tetranuclear nickel(II) compound [Ni4(L)4Cl4(H2O)3(C2H5OH)]·H2O (1) and a binuclear iron(III) compound Fe2(L)2Cl4 (2) (HL = 2-pyridinemethanol) have been prepared by solvothermal reaction of metal chloride and 2-pyridinecarboxaldehyde in C2H5OH, in which 2-pyridinecarboxaldehyde was in situ reduced to 2-pyridinemethanol. The single crystal X-ray diffraction analysis suggests that the cluster core of [Ni43-O)4] in 1 is formed by four Ni(II) and four alkoxide oxygen atoms at alternating corners, and the binuclear iron complex 2 is almost co-planar structure with alkoxide oxygen atom in μ2-mode. The magnetic studies reveal the ferromagnetic behavior for 1 and the anti-ferromagnetic interaction for 2.The solvothermal reaction of NiCl2 and FeCl3 with 2-pyridinecarboxaldehyde in C2H5OH solution at 100 °C can afford two types of polynuclear compounds in which the ligand 2-pyridinemethanol derived from the reduction of the 2-pyridinecarboxaldehyde and the alkoxide oxygen atoms acts as μ3- and μ2-linkage, respectively.Display Omitted► Two Ni2+ and Fe3+ complexes were obtained by in-situ solvothermal reaction. ► 2-pyridinecarboxaldehyde was in situ reduced to 2-pyridinemethanol. ► Ni complex is cubane-like formed by four Ni2+ and four alkoxide O atoms in μ3-mode. ► Fe complex is co-planar with alkoxide O atoms in μ2-mode. ► They display ferromagnetic and anti-ferromagnetic interactions, respectively.
Keywords: In-situ ligand synthesis; Crystal structure; Supramolecule; Magnetism;

The synthesis of a new multi-metallic porphyrin based on the meso-5,10,15-tris(4-pyridyl)-20-pentafluorophenyl porphyrin containing a copper(II) metal center, two ruthenium(II) bipyridyl complexes bound to two peripheral N-pyridyl nitrogens, and a platinum(II) dichloro complex bound to the remaining N-pyridyl nitrogen is presented. The new complex binds to plasmid DNA more efficiently than the well known anticancer drug cis-platin, as determined by gel electrophoresis. When solutions of the plasmid DNA in the presence of the new complex are irradiated with visible light the rate of binding of the complex to DNA is enhanced even further.A new multi-metallic complex combining a porphyrin with ruthenium(II) polypyridyl, a pentafluorophenyl substituent, a copper(II) metal center, and a platinum(II) moiety shows promise as a new DNA binding agent.Display Omitted► A new multi-metallic Cu/Ru/Pt porphyrin has been synthesized. ► This complex covalently binds to DNA with greater effect on gel migration than cis-platin. ► When irradiated with low energy light the complex binds to DNA at an increased rate.
Keywords: DNA binding; metalloporphyrin; photoinduced binding; porphyrin;

A new hydrazine-bridged thioantimonate Mn2Sb4S8(N2H4)2: Synthesis, structure, optical and magnetic properties by Yi Liu; Yufeng Tian; FengXia Wei; Michael Ser Chong Ping; Chuanwei Huang; Freddy Boey; Christian Kloc; Lang Chen; Tom Wu; Qichun Zhang (884-888).
A new thioantimonate [Mn2Sb4S8(N2H4)2] (1) was solvothermally synthesized by reacting Mn and Sb2S3 with S in hydrazine monohydrate solution. The single crystal structure analysis revealed that all Mn sites adopt distorted octahedral shapes and all Sb sites have either four-fold coordinated SbS4 configurations or square pyramidal SbS5 geometry. These polyhedra units are interconnected into two-dimensional layers via the sharing S atoms. These layers are further bridged into a novel three-dimensional framework by intra- and inter-layer hydrazine ligands. The compound 1 is a semiconductor with a band gap of 1.59 eV and displays paramagnetic behavior at high temperature and switches to antiferromagnetic ordering at 40 K.A new chalcogenide [Mn2Sb4S8(N2H4)2] (1) was synthesized by the hydrazine-hydrothermal method. Single-crystal X-ray diffraction analysis reveals that compound 1 features a novel three-dimensional network, in which two-dimensional chalcogenide layers are bridged by intra- and inter-layer hydrazine ligands. Optical study shows that compound 1 has a bandgap of about 1.59 eV. Magnetic measurements indicate that compound 1 displays paramagnetic behavior at high temperature and switches to antiferromagnetic ordering at 40 K.Display Omitted► Hydrazine-hydrothermal method to grow crystalline chalcogenides. ► Hydrizane-bridged three-dimensional framework Mn2Sb4S8(N2H4)2. ► The material has a bandgap at ~ 1.59 eV. ► The chalcogenide displays paramagnetic behavior at high temperature (from 40 to 300 K) and antiferromagnetic properties below 40 K.
Keywords: Chalcogenide; Crystal structure; Solvothermal synthesis; Magnetic property; Optical properties;

The hydrothermal reaction of Ln(III) nitrate, Mn(II) sulfate hydrate with 5-nitroisophthalic acid (H2NIPH) produced two novel metal organic frameworks (MOFs), [Ln2Mn(NIPH)4(H2O)4]·6H2O [Ln = Eu (1), Nd (2)], which represent the first examples of three-dimensional Ln(III)–Mn(II) heterometallic MOFs based on rod-shaped molecular building blocks (MBBs). In the structures, two LnO9 polyhedra and one MnO6 polyhedron are bridged in a corner-sharing fashion to form a trinuclear unit [Ln2MnO20], which is further connected to each other by carboxylate groups to give a [Eu2MnO20]-(O-C-O)2-[Eu2MnO20] heterometallic rod. The thermal properties and magnetic properties of 1 and 2 have been investigated in the solid state.The [Ln2Mn(NIPH)4(H2O)4]·6H2O [Ln = Eu (1), Nd (2)] represent the first examples of 3-D Ln(III)–Mn(II) heterometallic MOFs based on rod-shaped molecular building blocks.Display Omitted► Two three-dimension Ln(III)-Mn(II) hetrometallic metal organic frameworks. ► Rod-shaped molecular building block is composed of LnO9 polyhedra and MnO6 polyhedron in a corner-sharing fashion. ► The antiferromagnetic and ferromagnetic coupled interactions exist in compounds upon decreasing temperature. ► The thermal properties have been investigated.
Keywords: Heterometallic MOFs; Rod-shaped MBBs; Hydrothermal synthesis; Magnetic properties;

Three-dimensional porous metal–organic replica of natural mineral α-Al2O3 based on hexadentate triazine derivative by Chun-Yi Sun; Shuang Wang; Guang-Sheng Yang; Xin-Long Wang; Kui-Zhan Shao; Zhong-Min Su (893-896).
A non-interpenetrated 3D porous metal–organic framework [(CH3)2NH2]2[Cd(TATAT)2/3]·4DMF (1) (TATAT = 5,5′,5″-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)triisophthalate) has been successfully synthesized under solvothermal conditions and characterized by elemental analysis, TGA, and single-crystal X-ray diffraction analysis. Compound 1 exhibits α-Al2O3 (corundum) topology and represents the first metal–organic analog presently known with a natural material topology based on 6-connected organic ligand and tetrahedral metal ion. In addition, the thermal stabilities of the complex and the acid-treated product have been investigated and the results indicate that acid treatment is an efficient way for this compound to improve its thermal stability.A non-interpenetrated 3D porous metal–organic framework (1) has been successfully synthesized. 1 exhibits α-Al2O3 (corundum) topology and represents the first metal–organic analog presently known with a natural material topology which is based on octahedral organic ligand and tetrahedral single metal ion.Display Omitted► A non-interpenetrated 3D porous metal–organic frameworks (1) was synthesized. ► 1 is based on octahedral organic ligand and tetrahedral single metal ion. ► 1 exhibits peculiar α-Al2O3 (corundum) topology. ► Thermal stability of 1 and acid treated product have been determined. ► Acid treatment is a efficient way for 1 having a higher thermal stability.
Keywords: Metal–organic frameworks; α-Al2O3 topology; Porous; Natural material;

Two novel lineal d10 metal-organic frameworks with a ditopic flexible linker: Structures, blue luminescence and thermal stability by Iván Brito; Javier Vallejos; Alejandro Cárdenas; Matías López-Rodríguez; Michael Bolte; Jaime Llanos (897-901).
Two novel supramolecular Ag(I) complexes, {[AgL]NO3}n (1), and {[AgL]CF3SO3}n (2), (L) =  ethane-1,2-diyl bis(pyridine-3-carboxylate) have been prepared by self-assembly of Ag(I) salts with ethane-1,2-diyl bis(pyridine-3-carboxylate) (L) in THF/H2O system. The IR, TGA and elemental analysis have been recorded and both complexes were structurally characterized by X-ray crystallography confirming that complexes (1) and (2) are one-dimensional coordination polymers with lineal and helical chain motifs respectively. Solid emission spectra at room temperature of (1) and (2) show interesting blue phosphorescence with maximum intensity at 414 and 411 nm respectively, which are assigned to (LLCT) transition.The reaction of the flexible ligand, L (L) = ethane-1,2-diyl-bis-(pyridyl-3-carboxylate) with AgX (X = NO3, CF3SO3) under same experimental conditions allows to obtain coordination polymers with different properties such as structural motif, thermal stabilities and luminescent.Display Omitted►Anion effect in different structural motifs. ►Ag―Ag-interaction effect on luminescent properties. ►Different structural motifs' effect on the thermal stability.
Keywords: Coordination polymers; X-ray diffraction; Thermal analysis; Phosphorescence emission;

A new photochemical dehalogenation system mediated by macrocyclic nickel(II) complexes was developed. Using this system, which consists of a macrocyclic nickel(II) complex catalyst, triethanolamine (TEOA) as a sacrificial reductant, and the ruthenium complex [Ru(bpy)3](ClO4)2 as a photosensitizer, catalytic debromination of 1-bromo-4-t-butylbenzene in acetonitrile was effectively carried out. The catalytic capabilities of various macrocyclic nickel(II) complexes in debromination reactions were also elucidated.A new photochemical dehalogenation system mediated by macrocyclic nickel(II) complexes was developed. Using this system, which consists of a macrocyclic nickel(II) complex catalyst, triethanolamine (TEOA) as a sacrificial reductant, and the ruthenium complex [Ru(bpy)3](ClO4)2 as a photosensitizer, catalytic debromination of 1-bromo-4-t-butylbenzene in acetonitrile was effectively carried out.Display Omitted► New photochemical dehalogenation system mediated by macrocyclic nickel(II) complexes. ► Nickel(II) complexes acted as catalyst and [Ru(bpy)3]2+ as photosensitizer. ► Catalytic debromination of 1-bromo-4-t-butylbenzene was effectively carried out. ► Various macrocyclic nickel(II) complexes showed catalytic capabilities. ► These capabilities depended on the number and the positions of methyl groups.
Keywords: Photochemical dehalogenation; Nickel(II) complexes; Macrocyclic ligands; Catalytic reactions; Debromination;

A new organic amine templated 1D europium sulfate [H3O]2[(CH3)2NH2][Eu(SO4)3] 1 has been solvothermally synthesized and structurally characterized by single-crystal X-ray, IR and TGA. Structure analysis indicates that the structure of 1 exhibits a 1D chain structure compensated by protonated dimethylamine and water cations. The strong red fluorescence for 1 has been observed in the solid state.The structure of a new organic amine templated 1D europium sulfate [H3O]2[(CH3)2NH2][Eu(SO4)3] 1 exhibit a 1D chain structure compensated by protonated dimethylamine and water cations occluded in the helical [Eu–O–S]n chains. The strong red fluorescence for 1 has been observed in the solid state.Display Omitted► The first organic amine templated 1D europium sulfate has been synthesized. ► Compound 1 compensated by protonated dimethylamine and water cations. ► Compound 1 exhibit a 1D helical [Eu-O-S]n chains. ► The strong red fluorescence for 1 has been observed in the solid state.
Keywords: Solvothermal synthesis; Luminescence property; 1D; Europium sulfates;

Hexafluoroacetylacetonate (HFAA) is functionalized with 3-(triethoxysilyl)-propyl isocyanate (TEPIC) to achieve a new molecular building block HFAASi. Then two series ternary hybrid xerogels of rare earth ions (Eu3+, Tb3+, and Sm3+) with HFAASi and special terminal ligands bis(2-methoxyethyl)ether (BME) have been assembled through coordination bonds, whose photoluminescence are studied in details.Three kinds of ternary hybrid xerogel systems of rare earth ions (Eu3+, Tb3+, and Sm3+) with hexafluoroacetylacetonate (HFAA) derived building block HFAASi and bis(2-methoxyethyl)ether (BME) have been assembled through coordination bonds and show the photoluminescence property.Display Omitted► New ternary rare earth hybrid xerogels. ► Novel linkage of functionalized hexafluoroacetylacetonate. ► Luminescence in visible region. ► Coordination bonds assembly.
Keywords: Ternary rare earth hybrid xerogel; Hexafluoroacetylacetonate building block; bis(2-methoxyethyl)ether; Photoluminescence;

Synthesis, crystal structure and catalytic property of praseodymium(III) coordination polymer containing tetrazole-5-acetato(tza) anion ligands by Gao-Wen Yang; Dian-Yu Chen; Chun Zhai; Xiao-Yan Tang; Qiao-Yun Li; Feng Zhou; Zhu-Feng Miao; Jian-Ning Jin; Hong-Dan Ding (913-915).
A novel 1D coordination compound [Pr2(tza)3(H2O)6]n·4nH2O (1) (tza = tetrazole-5-acetato) was synthesized by the reaction of tetrazole-5-acetic acid with Pr(NO3)3·6H2O in the presence of KOH. This complex showed a specific and good catalytic behavior in the polymerization of styrene. The high molecular weight polymers with narrow molecular weight distributions in good yields were obtained within a few minutes.A novel 1D coordination compound [Pr2(tza)3(H2O)6]n·4nH2O (1) (tza = tetrazole-5-acetato) was synthesized by the reaction of tetrazole-5-acetic acid with Pr(NO3)3·6H2O under the presence of KOH. This complex showed a specific and good catalytic behavior in the polymerization of styrene. The high molecular weight polymers with narrow molecular weight distributions in good yields were obtained within a few minutes.Display Omitted► A novel 1D coordination compound [Pr2(tza)3(H2O)6]n·4nH2O (1) (tza = tetrazole-5-acetato) was synthesized by reaction of tetrazole-5-acetic acid with Pr(NO3)3·6H2O under the presence of KOH. ► This complex showed a specific and good catalytic behavior in the polymerization of styrene. ► The high molecular weight polymers with narrow molecular weight distributions in good yields were obtained within a few minutes.
Keywords: Praseodymium(III); Tetrazole-5-acetato; Coordination polymer; Crystal structure; Catalytic property;

A hexanuclear Ni(II) complex of 1-[(2-carboxymethyl)benzene]-3-[2-pyridine] triazene by Wei Li; Jin-Ye Chen; Wei-Quan Xu; Er-Xuan He; Shu-Zhong Zhan; De-Rong Cao (916-919).
A reaction of 1-[(2-carboxymethyl)benzene]-3-[2-pyridine]triazene (HL) and Ni(Ac)2⋅ 4H2O yields crystals of {Ni6L2L′23-OH)2(CH3O)2(Ac)2(H2O)4} 1 (L′ = 1-[(2-carboxyl)benzene]-3-[2-pyridine]triazene ion), which has been characterized by single-crystal and powder X-ray diffraction, vibrational spectroscopy, thermogravimetric (TG) analysis, as well as variable-temperature magnetic susceptibility. Complex 1 has a remarkable structure with unusual diversity of bridging groups including triazenide molecules, OH groups and –OCH3 groups. The magnetic susceptibility study reveals antiferromagnetic interaction between nickel(II) ions in the polynuclear complex.A reaction of 1-[(2-carboxymethyl)benzene]-3-[2-pyridine]triazene (HL) and Ni(Ac)2⋅4H2O yields crystals of {Ni6L2L′23-OH)2(CH3O)2(Ac)2(H2O)4} 1 (L′ = 1-[(2-carboxyl)benzene]-3-[2-pyridine]triazene ion), which has been characterized by single-crystal and powder X-ray diffraction, vibrational spectroscopy, and thermogravimetric (TG) analysis, as well as variable-temperature magnetic susceptibility.Display Omitted► Our interest focused on the design, synthesis and reactivity of new triazenide ligand. ► 1-[(2-carboxymethyl)benzene]-3-[2-pyridine]triazene (HL) was synthesized. ► The reaction of HL and Ni(Ac)2⋅4H2O gave a hexanuclear nickel(II) complex.
Keywords: Triazene; Polynuclear nickel complex; Crystal structure; Magnetic property;

A combined experimental and computational investigation on Tetrakis-μ-acetato-bis(acetamido)dicopper(II) and its application as a single source precursor for copper oxide by Manoj Trivedi; R. Nagarajan; Abhinav Kumar; Kieran C. Molloy; Gabriele Kociok-Köhn; Anna L. Sudlow (920-924).
The physico-chemical properties of the Tetrakis-μ-acetato-bis(acetamido)dicopper(II) [Cu(O2CCH3)2(CH3CONH2)]2 (1), have been thoroughly investigated via an integrated multi-technique experimental–computational approach. In the newly found orthorhombic compound, as revealed by low temperature single-crystal X-ray studies, the complex is present as centrosymmetrical dimeric unit, has a paddle-wheel conformation with four acetate ligands bridging two symmetry-related CuII ions. The distorted octahedral coordination environment around the CuII ion is completed by an oxygen atom from an acetamide ligand. The compound sublimates, without premature side decompositions, at 180 °C. The structural, electronic and thermal behavior of the neutral complex (1) has been investigated. The present study suggests application of [Cu(O2CCH3)2(CH3CONH2)]2 (1) as a precursor for copper-based materials by Chemical Vapor Deposition.The physico-chemical properties of [Cu(O2CCH3)2(CH3CONH2)]2, have been thoroughly investigated via an integrated multi-technique experimental–computational approach, which suggests applications of the compound as a precursor for copper-based materials by Chemical Vapor Deposition.Display Omitted► Tetrakis-µ-acetato-bis(acetamido)dicopper(II) synthesized using hydrothermal method. ► The complex was investigated via an integrated multi-technique experimental–computational approach. ► Study suggests applications of [Cu(O2CCH3)2(CH3CONH2)]2 as a precursor for copper-based materials by Chemical Vapor Deposition.
Keywords: Copper(II) complex; X-ray structure; Hydrogen bond interactions; TD-DFT; Chemical Vapor Deposition;

A novel Cu5 II cluster-based 3D magnetic framework with an overall S  = 1/2 spin ground state by Zhong-Yi Liu; Jing Chu; Bo Ding; Xiao-Jun Zhao; En-Cui Yang (925-928).
A 3D (3,8)-connected tfz-d framework with unusual Cu5 II clusters periodically extended by 5-nitroisophthalate (nip2−) ligands, {[Cu5(μ 3-OH)2(μ 2-H2O)2(H2O)4(nip)4]·5H2O}n (1), was hydrothermally synthesized and structurally characterized. Magnetically, the spin frustration in a vertex-sharing triangular aligned Cu5 II cluster leads essentially to an overall S  = 1/2 spin ground state of 1.A novel 3D CuII5 clusters-based tfz-d framework was hydrothermally synthesized, and the spin-frustration within the pentanuclear cluster leads to a S  = 1/2 spin ground state of 1.Display Omitted► A novel 3D tfz-d framework with CuII5 clusters was hydrothermally obtained. ► The nitro group of nip2- ligand is firstly observed to coordinate with metal ion. ► The spin frustration in triangular CuII5 cluster leads to a S  = 1/2 spin ground state.
Keywords: Metal-cluster based coordination polymer; Pentanuclear CuII cluster; Magnetism;

New tetranuclear macrocyclic complex: Crystal structure, magnetic property and DNA cleavage activity by Qingrong Cheng; Zhiquan Pan; Hong Zhou; Jingzhong Chen (929-933).
A new tetranuclear complex[Cu4L2(bipy)2](ClO4)2·H2O] has been obtained and fully characterized (where bipy = 4,4′-bipyridine, H2L is the macrocycle obtained from [2 + 2] condensation reaction between 2,6-diformyl-4-methylphenol and 1,3-diaminopropane). It exhibits a wheel-like configuration in which two bipy molecules connect two dinuclear [Cu2L]2+ units. The magnetic measurement of the complex reveals that there is a strong antiferromagnetic coupling (J  = − 383.88 cm− 1) between two Cu(II) ions in the macrocyclic unit and ferromagnetic interaction (j′ = 10.21) between the Cu(II) ions in two adjacent macrocyclic units. The interactions of the complex with calf thymus DNA were studied by UV–vis and CD spectroscopic techniques and the binding constant of between them is 1.74 × 104  M− 1.A new wheel-like tetranuclear copper complex has been obtained by template reaction. It exhibits wheel-like configuration in which two bipy molecules connect two dinuclear [Cu2L]2+ units. The magnetic measurement of the complex reveals that there is a strong antiferromagnetic coupling between two Cu(II) ions in the macrocyclic unit and ferromagnetic interaction between the Cu(II) ions in two adjacent macrocyclic units. The interactions of the complex with calf thymus DNA was studied by UV–vis and CD spectroscopic techniques.Display Omitted► Synthesize a new coordination dimer of Robson-type complex bridged by 4, 4′-bipy. ► Study the magnetic property, DNA binding and cleavage activity of the dimer. ► This is the the first example of dimer used as DNA cleavage agents.
Keywords: Tetranuclear macrocyclic complex; Magnetism; DNA cleavage activity;

bis-C(cage)-substituted 1,2-bis(aminomethyl)-1,2-dicarba-closo-dedocaborane hydrochloride was obtained from the reaction of 1,2-bis(phthalimidomethyl)-1,2-dicarba-closo-dodecaborane with sodium borohydride, followed by acid hydrolysis with glacial acetic acid. When the compound dissolved in DMSO, the easy degradation from the closo-stucture compound to corresponding nido-carborane derivative at room temperature occured.A mild pathway for the synthesis of an important functionalized carborane derivative bis(short-chain-amino) substituted o-carborane 1,2-bis(aminomethyl)-1,2-dicarba-closo-dodecaborane hydrochloride is reported, which include the reduction of 1,2-bis(phthalimidomethyl)-1,2-dicarba-closo-dodecaborane by sodium borohydride, followed by acid hydrolysis. The compound encounters convenient closo- to nido- transformation in DMSO at room temperature.Display Omitted► 1,2-bis(aminomethyl)-1,2-dicarba-closo-dedocaborane hydrochloride was synthesized. ► Compound obtained by sodium borohydride reduction and acid hydrolysis. ► Adding the gas and material slowly can restrain side reaction in acid hydrolysis process. ► Compound easily degraded in DMSO at room temperature.
Keywords: Bis-aminomethyl; Dicarbadodecaborane; Degradation; BNCT;

A new sensor based on luminescent terbium–organic framework for detection of Fe3+ in water by Song-Liang Cai; Sheng-Run Zheng; Jun Fan; Tian-Tian Xiao; Jing-Bo Tan; Wei-Guang Zhang (937-939).
A new terbium (III) coordination polymer {Tb3(μ 3-HPyIDC)4(H2O)8]∙NO3∙4H2O}n, which exhibits intense green luminescence, was prepared via solvothermal reaction. Interestingly, it still gives rise to green emission when dispersed in pure water. Its sensing abilities were investigated by addition of different cations such as Fe3+, Ba2+, Zn2+, K+, Na+, Mg2+, Ca2+, Fe2+, Mn2+, Co2+, Ni2+, Hg2+, and Cd2+ to water suspension of the assayed powder material. We discovered that only Fe3+ (detection limit 10− 4  M) can give rise to unique fluorescence changing from green to blue to this material. Spectroscopic analyses proved that the coordination interaction between Fe3+ ion and ligand led to this recognition process.A new luminescent terbium–organic framework with (3,4)-connected 2D network exhibits a high-sensitivity sensing function with respect to Fe3+, which can give rise to unique fluorescence changing from green to blue.Display Omitted► A Tb(III)-organic framework gives rise to green emission in pure water. ► The complex exhibits a highly selective fluorescent response towards Fe3+ ion. ► The luminescence of the complex changing from green to blue induced by Fe3+ ion.
Keywords: Sensor; Fe3+ ion; Luminescence; Terbium;

Facile condensation of one equiv. of the caged hydroxymethylphosphine Ad`PCH2OH (Ad` = C10H16O3) with ClPR2 (R = Ph, i Pr), in the presence of one equiv. of MCl2(cod) (M = Pt, Pd; cod = cycloocta-1,5-diene), afforded the five-membered chelate complexes cis-MCl2(Ad`PCH2OPR2) (1a, M = Pt, R = Ph; 1b, M = Pd, R = Ph; 2a, M = Pt, R =  i Pr) in reasonable to excellent yields. The X-ray structures of 1a and 2a have been determined, the latter using diffraction data collected at a synchrotron source. The M―P―C―O―P metallacycle remains intact even after stirring in CD3OD for 24 h at room temperature.Metal-assisted template condensation of Ad`PCH2OH and R2PCl (R = Ph, i Pr) with MCl2(cod) (M = Pt, Pd) affords the square planar nonsymmetric complexes MCl2(Ad`PCH2OPR2) in reasonable to high yields.Display Omitted► Metal-assisted condensation for new nonsymmetric phosphorus ligands. ► Structures verified in solution using NMR spectroscopy. ► Single crystal X-ray crystallography confirmed solid state structures in two cases. ► The M–P–C–O–P metallacycle is stable at room temperature in methanol.
Keywords: Crystal structure; Ditertiary phosphine; Palladium; Platinum; Template synthesis;

Solvothermal synthesis, structure and properties of a new 3-D Cu(I)–Gd(III) heterometallic coordination framework by Man-Sheng Chen; Yi-Fang Deng; Chun-Hua Zhang; Dai-Zhi Kuang; Xue Nie; Yang Liu (944-947).
A new 3d–4f heterometallic coordination polymer, [CuGd2(INAIP)3(HCOO)(H2O)3]·3H2O (1), [H2INAIP = 5-(isonicotinamido)isophthalic acid] has been synthesized and characterized by single crystal X-ray diffraction analysis. The results of structural analyses show that 1 has a two-fold interpenetrated 3D coordination framework with a rare sqc27 topology. In addition, thermogravimetric and magnetic properties were also investigated.A novel 3D two-fold interpenetrated coordination polymer, [CuGd2(INAIP)3(HCOO)(H2O)3]·3H2O (1), has been solvothermally synthesized and characterized. Complex 1 shows a rare sqc27 topology with weak antiferromagnetic coupling interaction between Gd2.Display Omitted► Three-dimensional two-fold interpenetrated coordination framework. ► Solvothermal synthesis effect on formation and structure of the Cu(I)-Gd(III) metal-organic framework. ► It shows a rare sqc27 topology.
Keywords: Heterometallic complex; Metal-organic framework; Solvothermal reaction; Magnetism;

A new 2D lanthanide-organic framework with 1D rod-shaped SBUs based on 4,6-dimethyl-5-nitroisophthalic acid has been solvothermally synthesized. The uncoordinated 4,4′-bipy ligands, which are trapped in the cavities by forming weak offset face-to-face pyridine–phenyl interaction with the wall of the cavities, play a template role in the formation of the 2D layer. To the best of our knowledge, this is the first 2D lanthanide-organic framework that synthesized by templated synthesis.A new 2D lanthanide-organic framework with 1D rod-shaped SBUs has been synthesized and characterized. The uncoordinated 4,4′-bipy were trapped in the cavities and played a template role in the formation of the complex.Display Omitted► We synthesized a new 2D lanthanide-organic framework containing large cavities. ► The uncoordinated 4,4′-bipy were trapped in the cavities. ► The 4,4′-bipy molecules template the formation of the 2D layer framework.
Keywords: Lanthanide; Templated synthesis; Cavity; 4,6-dimethyl-5-nitroisophthalic acid;

Two new metal coordination polymers [Zn(dpa)]n (1) and {[Zn2(dpa)(PyBIm)(H2O) (OH)]·1.5 (H2 O)}n (2) [H2dpa = Biphenyl-2,4′- dicarboxylic acid and PyBIm = 2-(4-Pyridyl)benzimidazole] have been synthesized and structurally characterized. Compound 1 features a 3D structure with a uninodal 4-connected (42.64) topology based on sod-type frameworks. Compound 2 exhibits a 2D (4,4) layer constructed from secondary building units (SBUs) of dinuclear zinc clusters.Two new metal coordination polymers [Zn(dpa)]n (1) and{[Zn2(dpa)(PyBIm)(H2O) (OH)]·1.5 (H2 O)}n (2) [H2dpa = Biphenyl-2,4′- dicarboxylic acid and PyBIm = 2-(4-Pyridyl)benzimidazole] have been synthesized and structurally characterized. Compound 1 features a 3D structure with a uninodal 4-connected (42.64) topology based on sod-type frameworks. Compound 2 exhibits a 2D (4,4) layer constructed from secondary building units (SBUs) of dinuclear zinc clusters.Display Omitted► We use rigid biphenyl dicarboxylates [2,4′-biphenyl-dicarboxylic acid] to construct new metal coordination polymers. Compound 1 features a 3D structure with a uninodal 4-connected (42.64) topology based on sod-type frameworks. Compound 2 exhibits a 2D (4,4) layer constructed from secondary building units (SBUs) of dinuclear zinc clusters. ► The luminescent properties of 1 and 2 in the solid state were investigated.
Keywords: Coordination polymer; Luminescence; Crystal structure; Zinc (II);

Mono- and dinuclear (η6-arene) ruthenium(II) benzaldehyde thiosemicarbazone complexes: Synthesis, characterization and cytotoxicity by Tameryn Stringer; Bruno Therrien; Denver T. Hendricks; Hajira Guzgay; Gregory S. Smith (956-960).
A series of mono- and dinuclear (η6-arene) ruthenium(II) complexes were prepared by reaction of thiosemicarbazone ligands derived from benzaldehyde and ruthenium(II) precursors of the general formula [Ru(η6-arene)(μ-Cl)Cl]2, where arene =  p- i PrC6H4Me or C6H5C3H6COOH. These complexes were characterized by NMR and IR spectroscopy, ESI-mass spectrometry and elemental analysis. The molecular structure of the mononuclear p-cymene complex was determined by X-ray diffraction analysis, revealing a pseudo-tetrahedral piano stool conformation and a bidentate N,S coordination mode of the thiosemicarbazone ligand. The complexes and ligands were evaluated for their in vitro cytotoxicity against the WHCO1 oesophageal cancer cell line.Mono- and dinuclear (η6-arene) ruthenium(II) complexes were prepared by the reaction of thiosemicarbazone ligands derived from benzaldehyde and ruthenium(II) precursors of the general formula [Ru(η6-arene)(μ-Cl)Cl]2. Selected complexes displayed moderate activity against the WHCO1 oesophageal cancer cell line.Display Omitted► Monomeric and dimeric thiosemicarbazone ligands were prepared. ► Mono- and binuclear ruthenium(II) arene thiosemicarbazone complexes were synthesized. ► Complexes show a pseudo-tetrahedral geometry and bidentate N,S ligand coordination. ► Selected compounds showed moderate in vitro cytotoxicity.
Keywords: Bioorganometallic chemistry; Arene ruthenium(II); Thiosemicarbazones; Anticancer drugs;

Suzuki cross-coupling of aryl bromides catalyzed by cyrhetrenylphosphine complexes of palladium (II) by Diego Sierra; César Zuñiga; Gonzalo E. Buono-Core; Fernando Godoy; A. Hugo Klahn (961-963).
The heterobimetallic Re–Pd complex (CO)3Re(η5-C5H4PPh2)PdCl2(NCMe) I and the chelated complexes (η5-C5H4PPh2)(CO)2PR3Re–PdCl2 (R = Me, II and R = OMe, III) were used as precatalyst for the Suzuki reaction. Complexes II and III containing a metal–metal bond were shown to be more efficient precatalyst for cross-coupling reaction of a wide range of aryl bromides electronically activated, unactivated and sterically hindered.The palladium-catalyzed Suzuki cross-coupling of aryl bromides and phenyl boronic acid has been investigated for the first time using heterobimetallic complexes based on phosphinocyrhetrene ligands and showed good catalytic activity.Display Omitted► Phosphinocyrhetrene–Pd(II) complexes are effective precatalyst for Suzuki reaction. ► Chelated bimetallic complexes with a Re―Pd bond, improve catalytic activity. ► A wide range of activated and unactivated substrates afford high conversions.
Keywords: Cyrhetrenylphosphine ligand; Heterobimetallic catalyst; Suzuki reaction;

2-Ferrocenyl-1,8-naphthyridine (1) and cis,cis,cis-dicarbonyl-dichloro-bis (2-ferrocenyl-1,8-naphthyridine) ruthenium(II) complex (2) have been synthesized and characterized by IR, 1H-NMR spectroscopy and elemental analysis. The structure of the compounds was determined by X-ray analysis. The complex (2) showed catalytic activity in the hydrogenation reaction of N-benzylideneaniline by hydrogen transfer with conversions between 89% and 33% for catalyst/substrate relations 200/1 and 400/1.The synthesis and characterization of new ruthenium(II) derived from 2-ferrocenyl-1,8-naphthyridine is reported. The complex was studied as catalysts in hydrogen of imine reaction in basic solution.Display Omitted► The cis, cis, cis-dicarbonyl-dichloro-bis (2-ferrocenyl-1,8-naphthyridine) ruthenium (II) complex is a very active catalyst in the hydrogenation of N-benzylideneaniline in basic media, with high conversions. ► The use of sodium hydroxide prevents the competitive reaction of hydrolysis.
Keywords: Ruthenium complex; Hydrogenation imine; Catalysts ruthenium;

Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing excess m-CPBA oxidant, with a second-order rate constant of (1.3 ± 0.2) × 102  M− 1  s− 1. The acid-catalyzed disproportionation heavily depends on the electron demand of the substituted aryl groups on the porphyrin macrocycle. The disproportionation equilibrium constants show drastic change for the three porphyrin systems.Direct conversion of oxoiron(IV) porphyrin to oxoiron(IV) porphyrin radical cation has been studied in three porphyrin systems. The acid-catalyzed disproportionation results in different observations depending on the electron demand of the substituted aryl groups on the porphyrin macrocycle.Display Omitted► Directly conversion of oxoiron(IV) porphyrin to oxoiron(IV) porphyrin radical cation. ► Acid-catalyzed disproportionation in three P450 model systems. ► Porphyrin ring electron demand effect on disproportionation equilibrium constants.
Keywords: Oxoiron; Disproportionation; Compound I; Compound II; P450 model;

Design and synthesis of chelating diamide sorbents for the separation of lanthanides by Glen E. Fryxell; Wilaiwan Chouyyok; Ryan D. Rutledge (971-974).
A nanoporous sorbent designed around chelating iminodiacetamide (“IDA-Amide”) moiety was made on mesoporous silica (MCM-41) and evaluated for lanthanide separations (Ce3+, Nd3+, Eu3+, Gd3+, and Lu3+). The effects of solution pH on lanthanide binding were studied, as well as sorption kinetics, and competition from other metal ions. The IDA-Amide SAMMS® demonstrated an interesting difference in the kinetics of sorption of the lanthanide ions in the order of Lu3+  > Eu3+  > Gd3+  > Nd3+  > Ce3+. The close proximity of the ligands in the IDA-Amide SAMMS® may allow for multiple metal–ligand interactions (“macromolecular chelation”).A nanoporous sorbent designed around chelating iminodiacetamide (“IDA-Amide”) moiety was made on mesoporous silica and evaluated for lanthanide separations. IDA-Amide SAMMS demonstrated an interesting difference in the kinetics of sorption of the lanthanide ions in the order of Lu3+  > Eu3+  > Gd3+  > Nd3+  > Ce3+.Display Omitted► In this study we prepared nanoporous sorbents made using chelating diamide ligands. ► IDA-Amide SAMMS were found to have good affinity for lanthanides. ► They were also found to bind the different lanthanides at different rates.
Keywords: Nanoporous sorbent; Lanthanide; Separations; Iminodiacetic; Chelation; Diamide;

Synthesis and crystal structure of the first five-membered ansa-metallacyclocumulene rac-(ebthi)Zr(η 4-t-Bu-C4-t-Bu) by Vladimir V. Burlakov; Yulia V. Nelyubina; Konstantin A. Lyssenko; Vladimir B. Shur; Perdita Arndt; Katharina Kaleta; Wolfgang Baumann; Uwe Rosenthal (975-977).
The zirconocene alkyne complex rac-(ebthi)Zr(η 2-Me3SiC2SiMe3) (1) reacts with 1,4-bis-tert-butyl-buta-1,3-diyne to yield the novel five-membered metallacyclocumulene rac-(ebthi)Zr(η 4-t-Bu-C4-t-Bu) (2) (ebthi = 1,2-ethylene-1,1′-bis(η 5-tetrahydroindenyl)), t-Bu =  tert-butyl). The structure of 2 was confirmed by X-ray studies.Synthesis and Crystal Structure of the First Five-membered ansa-Metallacyclocumulene rac-(ebthi)Zr(η 4-t-Bu-C4-t-Bu). The zirconocene alkyne complex rac-(ebthi)Zr(η 2-Me3SiC2SiMe3) (1) reacts with 1,4-bis-tert-butyl-buta-1,3-diyne to yield the novel five-membered metallacyclocumulene rac-(ebthi)Zr(η 4-t-Bu-C4-t-Bu) (2) (ebthi = 1,2-ethylene-1,1′-bis(η 5-tetrahydroindenyl), t-Bu =  tert-butyl). The structure of 2 was confirmed by X-ray studies.Display Omitted► The complex rac-(ebthi)Zr(η 2-Me3SiC2SiMe3) reacts with 1,4-bis-tert-butyl-buta-1,3-diyne. ► The first ansa-metallacyclocumulene complex is formed and characterised. ► The spectroscopic and structural data were compared with similar complexes.
Keywords: Zirconocene; ansa-metallocene; rac-(ebthi); Metallacyclocumulene; Crystal structure;

A new lanthanide metal-organic framework with (3,6)-connected topology based on novel tricarboxylate ligand by Jin Xu; Libo Sun; Hongzhu Xing; Zhiqiang Liang; Jihong Yu; Ruren Xu (978-981).
A new 3D lanthanide metal-organic framework with rare flu-3,6-C2/c topology, [Tb(CPEIP)(DMF)(H2O)]·2H2O (1) (DMF = N, N-dimethylformamide), has been synthesized using novel tricarboxylate ligand 5-((4-carboxyphenyl)ethynyl)isophthalic acid (H3CPEIP). It crystallizes in monoclinic space group C2/c. The structure is constructed from metallic 6-connected and organic 3-connected building units with point symbol of (426)2(446287102). The fluorescent properties of compound 1 and organic ligand were studied.A new 3D lanthanide metal-organic framework with rare flu-3,6-C2/c topology, [Tb(CPEIP)(DMF)(H2O)]·2H2O (1) (DMF = N, N-dimethylformamide), has been synthesized using novel tricarboxylate ligand 5-((4-carboxyphenyl)ethynyl)isophthalic acid (H3CPEIP). It possesses 3D cross-linked channels.Display Omitted► A new 3D lanthanide MOF has been synthesized using novel tricarboxylate ligand. ► The (3,6)-connected net of compound 1 has been rarely observed in MOFs. ► Compound 1 possesses three dimensional channel system.
Keywords: Metal-organic framework; Lanthanide; Luminescence; (3,6)-Connected topology;

The synthesis of a Keggin-type polyoxotungstate-coordinated diplatinum(II) complex, [(CH3)4N]3[α-PW11O39{cis-Pt(NH3)2}2], obtained by reaction of Keggin-type mono-lacunary polyoxotungstate, [α-PW11O39]7−, with cis-diamminedichloroplatinum(II) in an aqueous solution is described. The complex was characterized by elemental analysis, thermogravimetric/differential thermal analysis (TG/DTA), Fourier transform infrared (FTIR), ultraviolet-visible (UV–vis), and solution 1H, 31P, and 183W nuclear magnetic resonance (NMR) spectroscopy. The two cis-platinum(II) moieties, [cis-Pt(NH3)2]2+, were coordinated each to two oxygen atoms in a mono-vacant site of [α-PW11O39]7− with C s symmetry, and the cis-conformation was highly stable in dimethylsulfoxide and water.A Keggin-type polyoxotungstate-coordinated diplatinum(II) complex, [(CH3)4N]3[α-PW11O39{cis-Pt(NH3)2}2] (Me4N-1), has been synthesized. The two cis-platinum(II) moieties, [cis-Pt(NH3)2]2+, were coordinated each to two oxygen atoms in a mono-vacant site of [α-PW11O39]7− with C s symmetry, and the cis-conformation was highly stable in dimethylsulfoxide and water with no additives.Display Omitted► A Keggin-type polyoxotungstate-coordinated diplatinum(II) complex was synthesized. ► Two cis-platinum(II) moieties were coordinated each to two oxygen atoms with C s symmetry. ► The cis-conformation was highly stable in dimethylsulfoxide and water.
Keywords: Polyoxometalate; cis-platinum(II) moiety; Nuclear magnetic resonance; Stability;

A new open framework material based on designed semi-rigid T-shaped tricarboxylate ligand by Xin Zhang; Jin-Xia Yang; Jian Zhang; Jian-Kai Cheng; Ming-Ling Sun; Yuan-Gen Yao (986-989).
A new compound, namely [Cd3(L1)2(μ 2-H2O)2]n·3nH2O (1 H3L1 = 5-(benzonic-4-ylmethoxy)-isophthalic acid), containing one-dimensional (1D) foot-shaped channels was hydrothermally synthesized. It was a three-dimensional pillar-layered framework based on rod-shaped metal-carboxylate second building units (SBUs) and designed T-shaped polycarboxylate ligand. Remarkably, 1D zigzag water chains directed by hydrogen bonds were captured in the channels, further stabilizing the whole framework. Moreover, this compound exhibits strong blue photoluminescence at room temperature.Presented here is a new three dimensional (3D) open Cd(II) coordination polymer, [Cd3(L1)2(μ 2-H2O)2]n·3nH2O (1 H3L1 = 5-(benzonic-4-ylmethoxy)-isophthalic acid), which captures a one dimensional (1D) zigzag water chain in the channels and exhibits strong blue photoluminescence at room temperature.Display Omitted► In this work, we designed and synthesized a new semi-rigid T-shaped tricarboxylate ligand,5–(benzonic–4–ylmethoxy)–isophthalic acid (H3L1). ► The hydrothermal reaction of Cd(OAC)2•2H2O with H3L1 lead to a new open cadmium(II) compound. ► One-dimensional zigzag water chains were captured in the foot-shaped channels.
Keywords: Hydrothermal synthesis; Pillar-layered framework; T-shaped ligand; Water chain;

Polymeric ketopiperazinediacetate complexes [M(kpda)(H2O)2]n·nH2O (M = Cu, 1; Zn, 2. H2kpda = ketopiperazinediacetic acid, C8H12N2O5) were obtained from the reactions of copper chloride and zinc nitrate with ethylenediaminetriacete at pH 5.0 (H3ed3a = ethylenediaminetriacetic acid), where ed3a is in equilibrium with amidation product of kpda. 1 or 2 consists of a monomeric neutral unit [M(kpda)(H2O)2]n, where ketopiperazinediacetate anion serves as bridged ligand through the amine nitrogen and the acetate oxygen forming a glycinate metallocycle, and the other acetate coordinates bidentately with the neighboring metal atom. The former could be converted to [CuII(ox)(phen)(H2O)]·H2O (3) after the addition of phenanthroline (H2ox = oxalic acid, phen = phenanthroline), which shows degradation of ethylenediaminetriaceta, where [CuI(phen)2Cl]·6H2O (4) and [CuII(phen)2(H2O)](NO3)2 (5) were isolated in the reaction sequence.Ethylenediaminetriaceta is degradated to oxalate by copper salt and phenanthroline, where part of Cu2+ is reduced to Cu+. Polymeric ketopiperazinediacetate complexes [M(kpda)(H2O)2]n·nH2O were obtained from the reaction of copper or zinc salt and ethylenediaminetriacete at pH 5.0.Display Omitted► Ethylenediaminetriaceta is degradated to oxalate by copper salt and phenanthroline. ► Polymeric ketopiperazinediacetate complex [Cu(kpda)(H2O)2]n·nH2O was isolated. ► Zinc ketopiperazinediacetate is isomorphous with copper complex. ► Phenanthroline copper(I) chloride was isolated as a reduced product in the reaction.
Keywords: Ketopiperazinediacetic acid; Ethylenediaminetriacetic acid; Zinc; Copper; Degradation; Crystal structure;

Fe(II) coordination polymers: Structures and surface photoelectric properties by Lei Li; Shu-Yun Niu; Dan Li; Jing Jin; Yu-Xian Chi; Yong-Heng Xing (993-996).
Two new Fe(II) coordination polymers, [Fe(dcbp)(H2O)2]n 1 and [Fe(pdc)(H2O)2]n∙nH2O 2 (H2dcbp = 4,4′-dicarboxy-2,2′-bipyridine, H2pdc = pyridine-2,5-dicarboxylic acid), were synthesized by hydrothermal method and characterized by IR, UV–Vis absorption spectra, elemental analysis, electron paramagnetic resonance spectra and X-ray single crystal diffraction. The surface photoelectric properties of Fe(II) coordination polymers were discussed emphatically by surface photovoltage spectroscopy (SPS). The structural analyses indicate that 1 is 3D coordination polymer bridged by dcbp2− groups and 2 is 2D layer structure bridged by pdc2− groups. The results of SPS show that there are photoelectric responses in the range of 300–550 nm, which reveals that they all possess photoelectric conversion properties. By the comparison and analysis, it is found that the dimension, species of ligands and coordination micro-environment of the Fe(II) ions should affect the results of the SPS. The SPS were associated with the UV–Vis absorption spectra.Two new Fe(II) coordination polymers were synthesized and characterized. Structural analyses indicate that 1 is 3D structure and 2 is 2D structure. The surface photo-electric properties of Fe(II) polymers were studied by SPS. The dimension, species of ligand and coordination micro-environment should affect the SPS.Display Omitted► Two Fe(II) polymers with 3D and 2D structures were reported. ► The surface photoelectric properties of Fe(II) polymers were studied by SPS. ► Two polymers all possess photoelectric conversion properties. ► The dimension, species of ligands and coordinated micro-environment affect the SPS.
Keywords: Fe(II) coordination polymer; Structure; Surface photovoltage spectroscopy;

On the basis of triangular-shaped [Mn3O] secondary building units, a novel two-dimensional (2D) manganese(III) complex, [NaMnIII 3O(sao)3(btec)0.5(H2O)3]·1.25H2O (1) (H2sao = salicylaldoxime, H4btec = benzene-1,2,4,5-tetracarboxylate acid), was synthesized and structurally characterized. The structure of 1 consists of 2D coordination polymer based on [Mn3O] units bridged by sodium ions and benzene-1,2,4,5-tetracarboxylate groups. Magnetic data analysis shows that antiferromagnetic couplings exist between the manganese(III) ions in [Mn3O] subunit of complex 1.Display Omitted► Using Na+ ion bridges its adjacent [Mn3O] units to 1D zigzag chain along b-axis. ► The 1D array is connected by btec4− ligands to a 2D network. ► Antiferromagnetic couplings exist between the manganese(III) ions in [Mn3O] unit.
Keywords: Coordination polymer; Two-dimensional; Triangular units; Crystal structure; Magnetic properties;

We report on the ionothermal synthesis of a novel two-dimensional (2D) cadmium metal organic framework, namely, [Emim][CdBr(1,4-NDC)] (1) (Emim = 1-ethyl-3-methylimidazolium, 1,4-NDCH2  = 1,4-naphthalenedicarboxylic acid) using an ionic liquid (IL) [Emim]BF4 or mixed ILs of [Emim]BF4 and [Emim]Br both as solvent and template. Single-crystal X-ray diffraction reveals that the structure features an anionic two-dimensional network based on the paddle wheel-like cluster. The imidazolium cations acting as charge compensating agent intercalate into the interlayer spaces. The current result is the first example of ionothermal synthesis of 1,4-NDC based metal organic framework. The thermal and photoluminescent properties have also been investigated.A novel cadmium metal organic framework [Emim][CdBr(1,4-NDC)] (1) (Emim = 1-ethyl-3-methylimidazolium, 1,4-NDCH2  = 1,4-naphthalenedicarboxylic acid) has been ionothermal synthesized in [Emim]BF4 and added KBr or in mixed ILs of [Emim]BF4 and [Emim]Br. The structure features an anionic 2D network based on the paddle wheel-like cluster.Display Omitted► Affect the formation/crystallization of MOF in IL by adding KBr or another IL. ► The first 1,4-NDC based MOF synthesized via ionothermal method. ► The first anionic 2D network based on the cadmium paddle wheel-like cluster.
Keywords: Ionic liquid; Ionothermal synthesis; Paddle wheel; Metal-organic framework; Crystal structure;

Mixed pentasupertetrahedral P1 and supertetrahedral T2 clusters as building units to create two-dimensional indium chalcogenides open framework by Chuan-Yu Chen; Chun-Chang Ou; Hsiu-Fuan Huang; Jeng-Horng Cheng; Chung-Sung Yang (1004-1009).
A new two dimensional open framework indium chalcogenide [In12S21(Se)3H2], NCYU-5, constructed from pentasupertetrahedral P1 clusters, [In8S14(Se1/2)3H], and supertetrahedral T2 clusters, [In4S7(Se1/2)3H], has been prepared through hydrothermal method. Each T2 cluster is jointed with three P1 clusters via Se atoms to form an infinite two dimensional structure stacked along the crystallographic c axis. The ion-exchange studies show that the guest molecules (TMDP) can be exchanged by monocations (Na+, K+), and dications (Mg2+, Ca2+, Sr2+, Ba2+). In the typical exchanged solids by Ba2+ cations, the quantitative microanalysis data for the atomic ratio (Ba/Se) of Ba (1.86%) and Se (15.42%) is 12.05%. The luminescent output from the NCYU-5 cluster exhibits a temperature-dependent shift. A shift from λmax  = 433 nm to λmax  = 450 nm occurs as temperature increases from 77 K to 298 K.A new two dimensional open framework indium chalcogenide [In12S21(Se3)H2] is prepared, in which each T2 cluster [In4S7(Se1/2)3H] is jointed with three P1 clusters [In8S14(Se1/2)3H] via Se atoms to form an infinite two dimensional structure stacked along the crystallographic c axis.Display Omitted► A new 2-D open framework [In12S21(Se)3H2], NCYU-5, is constructed from P1, and T2 clusters. ► The guest molecule (TMDP) can be exchanged by (Na+, K+), and (Mg2+, Ca2+, Sr2+, Ba2+) up to (Ba/Se) =12.05%. ► The luminescent output from the NCYU-5 exhibits a shift from λmax = 433 nm (77K) to λmax = 450 nm (298 K).
Keywords: Hydrothermal system; Tetrahedral cluster; Open framework; Chalcogenides;

Oxidation of a wide range of cyclic and acyclic olefins with tetra-n-butylammonium periodate shows different orders of catalytic activity for a series of electron-rich and electron-deficient Mn-porphyrins in oxidation of various alkenes. While the Mn(III) complex of meso-tetra(4-thiomethoxyphenyl)porphyrin, MnT(4-SCH3P)P(OAc), has the highest activity among the series, the β tetra-brominted derivative shows the lowest catalytic efficiency for the oxidation of the used olefins with the exception of cis- and trans-stilbene. The results clearly show that the electron-withdrawing effects of meso- and β-substituents may increase or decrease the catalytic activity of Mn-porphyrins in the case of different olefins.Oxidation of a wide range of cyclic and acyclic olefins with tetra-n-butylammonium periodate in the presence of imidazole and a series of electron-rich and electron-deficient Mn(III) meso-tetraarylporphyrins shows higher or comparable catalytic efficiencies for the electron-rich Mn-porphyrins compared with the electron-deficient ones.Display Omitted► Electron-rich Mn(III)-porphyrins as efficient as the electron-deficient ones. ► Unusual instability of Mn(III) meso-tetraarylporphyrin with para-NO2 groups. ► Different substituent dependence of catalytic activity for various olefins. ► High efficiency of MnT(4-SCH3P)P(OAc) in oxidation of olefins with periodate.
Keywords: Electron-rich and electron-deficient Mn-porphyrins; Oxidation; Olefins; Tetra-n-butylammonium periodate;

Porphyrin based microscopic crystalline rods have been synthesized from mixed building blocks. Both pyridine and hydroxide are prerequisite functionalities to generate crystalline materials. Porphyrin building blocks containing just pyridyl or hydroxy groups do not interact themselves and the formation of amorphous solids is observed.New class of porphyrin based microscopic crystalline rods has been synthesized from mixed building blocks. Both pyridine and OH are prerequisite functionalities in order to generate intermolecular interactions to produce crystalline objects, and those porphyrin building blocks containing just pyridyl or OH result amorphous aggregates.Display Omitted► New class of porphyrin based microcrystalline rods has been synthesized. ► Simple mixing of two different porphyrins building blocks leads to produce microscopic rods. ► Both pyridine and OH are prerequisite functionalities to produce crystalline objects.
Keywords: Microscopic crystal; Building block; Porphyrin; Amorphous;

The complexation reactions between metal(II) salts and a calix[4]arene derivative (1) with pendant arm Schiff bases which contain azine functionalities are described. The calix[4]arene derivative 1 is weakly fluorescent, but this fluorescence is quenched when it is deprotonated by base. The fluorescence only returns, and is in fact greatly enhanced, in the presence of zinc(II) ions.The calix[4]arene derivative 1 is weakly fluorescent. The fluorescence is greatly enhanced in the presence of zinc(II) ions only.Display Omitted► Much effort has gone into measuring both the concentration and distribution of Zn(II) in cells. ► This has resulted in a small number of zinc-selective fluorescent sensors. ► Despite this development, almost all sensors developed suffer from competitive bindings. ► Recently, we have devised a series of rigid calix[4]arene derivatives. ► This paper focuses on the complexation reactions of one derivative and its fluorescent properties.
Keywords: Fluorescence; Calix[4]arene; Schiff base; Zinc;

Novel nickle thiogermanates [Ni(trien)2]2Ge4S10 (1) (trien = triethylenetetramine) and [{Ni(tepa)}2(μ-Ge2S6)] (2) (tepa = tetraethylenepentamine) were respectively synthesized by the reaction of NiCl2·6H2O, GeO2 and S in trien and tepa under solvothermal conditions. The adamantane-like [Ge4S10]4− anion in 1 is composed of four GeS4 tetrahedra sharing the corners with three other tetrahedra via S2− bridges. 1 is the first example of damantane-like [Ge4S10]4− anion with transition metal complex as the counter cation. The bimeric [Ge2S6]4− anion in 2 is constructed by two GeS4 tetrahedra sharing a common edge. It acts as a μ-Ge2S6 ligand with the trans terminal S atoms to connect two [Ni(tepa)]2+ cations into the neutral complex 2. The syntheses of 1 and 2 show the influence of different ethylene polyamines on the formation of thiogermanates in the presence of transition metal. 1 and 2 exhibit semiconducting properties with the band gap E g at 2.31 and 2.48 eV respectively.Novel nickle thiogermanates [Ni(trien)2]2Ge4S10 and [{Ni(tepa)}2(μ-Ge2S6)] were solvothermally prepared with coordinative amines trien and tepa as templates. The syntheses of two compounds show the different structure-directing effects of ethylene polyamines on the formatin of thiogermanates in the presence of transition metal under solvothermal conditions.Display Omitted► New nickle thiogermanates [Ni(trien)2]2Ge4S10 (1) and [{Ni(tepa)}2(μ-Ge2S6)] (2) were prepared. ► Templates trien and tepa exhibit different structural directing effects. ► 1 presents the first example of damantane-like [Ge4S10]4– anion with transition metal counter cation.
Keywords: Nickle; Thiogermanates; Ethylene polyamine; Solvothermal synthesis; Crystal structure;

The reaction of dimethyldi(4-N,N-dimethylaminophenyl)silane (1) and chloroplatinic acid hexahydrate was carried out in acetone (ace). A complex salt, [H(dma)]2(PtCl6)·0.5ace (2·0.5ace) (dma  =  N,N-dimethylphenylamine), was obtained and characterized by Single-crystal X-ray diffraction. At the same time, byproducts (4-dimethylaminophenyl)dimethylsilanol (3), dma, 4-(dimethylphenyl silyl)-N,N- dimethylaniline (4), and 1,3-Bis(4-(dimethylamino)phenyl)-1,1,3,3-tetra-methyldi- siloxane (5), structurally confirmed by FT-IR, 1H NMR, 13C NMR, 29Si and ESI MS NMR spectra, were found. This indicates that the cleavages of Si–C and C–N bonds of 1 in the reaction occurred. In addition, the reaction mechanisms were referred.The reaction of dimethyldi(4-N,N-dimethylaminophenyl)silane (1) and chloroplatinic acid hexahydrate was carried out in acetone (ace). A complex salt, [H(dma)]2(PtCl6)·0.5ace (2·0.5ace) (dma  =  N,N-dimethylphenylamine), was obtained and characterized by Single-crystal X-ray diffraction. Its supramolecular structure was built through the hydrogen bond self-assembly, with a combination type in the molecule structure where anions and cations are staggered with respect to each other. The existence of dma indicates the cleavage of Si–C bond of 1 in the reaction occurred.Display Omitted► Complex salt [H(dma)]2(PtCl6)·0.5ace (2·0.5ace) was prepared unexpectedly. ► The crystal structure of 2·0.5ace shows the intramolecular neutralization effect. ► Proposed reaction mechanism shows the Si–C bond cleavage in common organic solvent.
Keywords: Dimethyldi(4-N,N-dimethylaminophenyl)silane; Chloroplatinic acid hexahydrate; Si–C bond cleavage; C–N bond cleavage; σ-complex;

Electrochemical preparation and photoluminescence of Y1.95Eu0.05O3 hierarchical nanosheets by Peng Zhang; Teng Zhai; Xihong Lu; Peng Liu; Yexiang Tong (1032-1035).
Large scale Y1.95Eu0.05O3 hierarchical nanosheets were synthesized from aqueous solution containing Y(NO3)3, Eu(NO3)3, and NH4NO3 with a current density of 2.0 mA·cm− 2 at 343 K via a simple and efficient electrodeposition method. The H2 gas bubbles functioning as a dynamic template are responsible for the growth of ordered Eu doped Y2O3 nanosheets. The thickness of these nanosheets in the range of 5–20 nm, and Y1.95Eu0.05O3 nanosheets with the cubic phase are obtained after calcining at 600 °C for 1 h in air. The correlation between the structure and the photoluminescence properties of the as-prepared and calcined nanosheets was also investigated.Herein, a large scale of Y1.95Eu0.05O3 nanosheets with hierarchical structure were assembled by a facile and hard-template-free electrodeposition. As shown in Fig. 3, H2 bubbles obtained play an important role as dynamic template in the whole process of electrodeposition. And insets SEM show this growth process of nanosheets.Display Omitted► Thin and uniform Y1.95Eu0.05O3 nanosheets were synthesized by electrochemistry method. ► A possible growth mechanism was proposed, in which the H2 bubbles play a role as a dynamic template. ► Crystalline Y1.95Eu0.05O3 was obtained after calcining. ► The structure and unique luminescent properties of the Y1.95Eu0.05O3 nanosheets have been investigated.
Keywords: Electrodeposition; Luminescence; Phase transformation; Nanosheets; Y1.95Eu0.05O3;

Synthesis, crystal structure and magnetic property of an iron(III) coordination polymer with N-acyl-salicylhydrazide ligand by Suni Qin; Chao Zu; Zilu Chen; Wanyun Huang; Jiangke Qin; Fupei Liang (1036-1038).
A one-dimensional coordination polymer of iron(III) with N-dehydroabietoyl-salicylhydrazide (H3L) ligand, [Fe(HL)Cl(CH3OH)]n·nCH3OH (1), was synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectra analysis. The N-dehydroabietoyl-salicylhydrazide ligand in the compound is doubly deprotonated and acts as a tetradentate ligand to Fe(III) ions in tridentate-monodentate/back-to-back fashion, giving rise to a linear chain structure. The 1D chain is further extended to 2D supramolecular network by intermolecular hydrogen bonds. The magnetic study of the compound indicates an antiferromagnetic coupling interaction between Fe(III) ions.The title iron(III) compound with chiral N-dehydroabietoyl-salicylhydrazide ligand presents 1D chain structure and displays an antiferromagnetic coupling interaction between Fe(III) ions.Display Omitted►A 1D iron(III) chain was obtained from chiral N-dehydroabietoyl-salicylhydrazide ligand. ►The dianion ligand binds to Fe(III) ions in tridentate-monodentate/back-to-back mode. ►The formation of 1D chain can be ascribed to the steric effect of the N-acyl group of ligand. ►The title compound presents an antiferromagnetic coupling interaction.
Keywords: Coordination polymer; Iron(III); N-acyl-salicylhydrazide; Crystal structure; Magnetic property;

Two new coordination compounds [Ag6(NHdmpym)2(dppm)4] (1·4ClO4) and [Ag4(NHpym)2(dppm)2] (2·2ClO4·2DMF) (NH2dmpym = 2-amino-4, 6-dimethylpyrimidine, NH2pym = 2-aminopyrimidine, dppm = bis(diphenylphosphino)methane, DMF =  N, N-dimethylformamide) have been synthesized under the ammoniacal conditions and structurally characterized. In 1 and 2, NH2dmpym and NH2pym ligands are deprotonated and show rare μ4-N 1:N 1:N 2 and μ3-N 1:N 2 coordination modes, respectively. The bridging dppm ligand combines the N-donor ligands to give 1 and 2 triangle Ag3 and rectangle Ag4 cores, respectively. The resulting Ag3 metallacycle is a scalene triangle with an average Ag···Ag distance of 3.1043(9) Å. The Ag4 metallacycle is an irregular rectangle with a shorter and a longer Ag···Ag distances of 2.8852(15) and 3.3202(13) Å, respectively. The structural variances between 1 and 2 are caused by the ratios of metal and ligands and substituent group effect. In addition, 1 and 2 exhibit blue photoluminescence which may be assigned to ligand-to-metal charge transfer (LMCT) transition.Two novel coordination compounds [Ag6(NHdmpym)2(dppm)4] (1·4ClO4) and [Ag4(NHpym)2(dppm)2] (2·2ClO4·2DMF) (NH2dmpym = 2-amino-4, 6-dimethylpyrimidine, NH2pym = 2-aminopyrimidine, dppm = bis(diphenylphosphino)methane, DMF = N, N-dimethylformamide) were synthesized and structurally characterized. The bridging dppm ligand combines the N-donor ligands to give 1 and 2 triangle Ag3 and rectangle Ag4 cores, respectively. Moreover, the emission behaviors of them were discussed.Display Omitted► Two novel silver coordination compounds were synthesized and characterized. ► The structures of these complexes were confirmed by X-ray crystallography. ► NHdmpym and NHpym show rare μ4-N 1:N 1:N 2 and μ3-N 1:N 2 coordination modes, respectively. ► The structural diversity as well as the photoluminescent properties were also discussed.
Keywords: Silver(I); 2-Amino-4, 6-dimethylpyrimidine; 2-Aminopyrimidine; Bis(diphenylphosphino)methane; Ag···Ag interaction; Photoluminescence;

New types of the germanium-capped clathrochelate iron(II) and cobalt(III) tris-dioximates: The synthesis, structure and electrochemical properties by Yan Z.Voloshin; Sergey V. Korobko; Alexander V. Dolganov; Valentin V. Novikov; Anna V. Vologzhanina; Yurii N. Bubnov (1043-1047).
The first bis-germanium-capped cobalt(III) and mixed germanium-boron-cross-linked iron(II) tris-dioximate clathrochelates were obtained and characterized using elemental analysis, UV–vis, IR, MALDI-TOF mass, 1H, 19F and 13C{1H} NMR spectra (for both the cobalt(III) and iron(II) complexes) as well as by X-ray diffraction crystallography (for the iron(II) macrobicycle).The first mixed boron-germanium-capped iron(II) clathrochelate with non-equivalent cross-linking groups and the bis-germanium-containing cobalt(III) complex were synthesized by transmetallation of the corresponding antimony-capped clathrochelate iron(II) and cobalt(III) precursors with IGe(CF3)3 and characterized using elemental analysis, spectral and electrochemical data as well as by X-ray diffraction crystallography (for the iron(II) complex).Display Omitted►Mixed boron-germanium-capped iron(II) clathrochelate was obtained by transmetallation. ►Boronantimony-capped macrobicyclic precursor undergoes transmetallation with IGe(CF3)3. ►Bisantimony-capped cobalt(III) clathrochelate undergoes transmetallation with IGe(CF3)3. ►The electrochemically generated oxidized clathrochelates are stable in CVA time scale.
Keywords: Macrocycles; Iron complexes; Cobalt complexes; Germanium complexes; Transmetallation; Ligand reactivity;

An efficient and room temperature synthesis of Fe3+ doped chlorocadmiumphosphate molecular sieves: Spectroscopic, thermal and powder XRD investigations by Ch. Rama Krishna; Ch. Venkata Reddy; U.S. Udayachandran Thampy; Y.P. Reddy; P. Sambasiva Rao; R.V.S.S.N. Ravikumar (1048-1051).
This paper mainly reports on the structural investigations of Fe3+ doped chlorocadmiumphosphate CdHPO4Cl·[H3N(CH2)6NH3]0.5 nanocrystals prepared at room temperature by organic amine templated method. Synthesized crystals are characterized by various spectroscopic techniques. From the powder X-ray diffraction patterns, the crystal system is indexed to monoclinic unit cell with lattice parameters a = 13.533, b = 15.008, c = 10.363 Å and β = 118.3°. The average size of the crystallite evaluated is 110 nm. FT-IR spectrum contains absorption bands related to organic amine and phosphate ions. The thermal analysis indicates that the inorganic framework collapses above 300 °C, after the removal of the organic amine template. From optical absorption and EPR studies the crystal field, Racah parameters and g values suggested that the doped Fe3+ ions entered the network at distorted octahedral site.Fe3+ ions doped chlorocadmiumphosphate CdHPO4Cl [H3N(CH2)6NH3]0.5 crystals are grown at room temperature by organic amine template method. Thermal analysis of the these crystals showed that the structure of the complex is stable up to 300 °C after that the structure of the complex collapsed due to the decomposition of organic amine HMDA.Display Omitted► This method is simple to synthesize MOF materials at room temperature. ► The prepared samples are highly crystalline and stable up to 300 °C temperature. ► These materials are used in the fields of catalysis. ► This method of preparation is eco-friendly and green synthesis.
Keywords: Molecular sieve crystals; Low temperature chemical synthesis; Spectroscopic characterization; Powder X-ray diffraction; Thermal analysis;

A novel 2-D organic–inorganic hybrid tetra-CoII-substituted sandwich-type Keggin germanotungstate {[Co(dap)2(H2O)]2[Co(dap)2]2[Co4(Hdap)2(B-α-HGeW9O34)2]}·7H2O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectrum, UV spectrum, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Structural analysis shows that 1 displays a rare 2-D (4,4)-topological network constructed by tetra-CoII-substituted sandwich-type Keggin germanotungstate units and [Co(dap)2]2+ bridges. To our knowledge, 1 represents the first 2-D organic–inorganic hybrid cobalt-substituted sandwich-type polyoxotungstate. Magnetic preperties of 1 have been investigated. The decrease of the product of the molar magnetic susceptibility at higher temperatures results from the spin-orbit coupling of the CoII ion and/or the antiferromagnetic interactions whereas the maximum at the lower temperatures is indicative of the ferromagnetic interactions within the tetranuclear CoII spin cluster in the sandwich belt.A novel 2-D organic–inorganic hybrid tetra-CoII-substituted sandwich-type Keggin germanotungstate has been hydrothermally synthesized and structurally characterized. Its magnetic preperties have been investigated.Display Omitted► Sandwich-type Keggin germanotungstate. ► 2-D organic–inorganic hybrid tetra-CoII-substituted sandwich-type polyoxometalate. ► 2-D (4,4)-topological network consisting of sandwich-type units. ► The ferromagnetic interactions within the CoII spin cluster. ► The spin-orbit coupling of the CoII ion.
Keywords: Polyoxometalate; Polyoxotungstate; Germanotungstate; Sandwich-type structure;

Simultaneous coordination of a ketone by two cadmium(II) ions and conversion to its gem-diolate(− 1) form by Eugenia Katsoulakou; Vlasoula Bekiari; Catherine P. Raptopoulou; Aris Terzis; Evy Manessi-Zoupa; Annie Powell; Spyros P. Perlepes (1057-1060).
Reaction of Cd(NO3)2∙ 4H2O and di-2-pyridyl ketone [(py)2CO] in dry MeCN led to complex [Cd2(NO3)4{(py)2CO}2] (1) in which the ketonic grouping of each organic ligand bridges the two CdII atoms. Complex 1 is extremely reactive towards nucleophiles; it reacts with H2O giving the cubane cluster [Cd4(NO3)4{(py)2C(OH)(O)}4] (2) possessing the 3.3011 (Harris notation) gem-diolate(− 1) form of the ligand. Upon excitation at 380 nm, solid 1 displays blue green photoluminescence at room temperature.Electrophilic activation of the carbonyl group of di-2-pyridyl ketone with two Cd(II) ions enhances its reactivity toward water leading to a cubane cluster possessing the gem-diolate(− 1) form of the ligand which bridges three metal ions.Display Omitted► The first Cd(II) complex containing the ketone form of di-2-pyridyl ketone is reported. ► The bridging carbonyl group is transformed into its gem-diolate(− 1) form. ► A cubane Cd(II) cluster has been prepared and characterized. ► The Cd(II)/di-2-pyridyl ketone complex exhibits blue-green photoluminescence.
Keywords: Cadmium(II) complexes; Cubane clusters; Di-2-pyridyl ketone; Electrophilic activation of carbonyl groups; Photoluminescent cadmium(II) complexes;

Synthesis, structure, ion-exchange and fluorescence of a novel two-dimensional niobium fluorophosphate with 4.8-net layer by Yu-Quan Feng; Dong-Fang Qiu; Zhi-Guo Zhong; Ke-Cheng Liu; Hong-Wei Wang (1061-1064).
A novel niobium fluorophosphate (NH4)2(Nb3P4O19F3)(H2en)2·H2O (1) has been synthesized by two-step hydrothermal method and characterized by elemental analyses, IR spectra, EDS analysis, PXRD, TG analysis and single-crystal X-ray diffraction. Compound 1 contains a novel two-dimensional 4.8-net layer constructed from the strict alternation of 4-connected NbO5F octahedra and 3-connected PO4 tetrahedra. 1 represents the first niobium fluorophosphate with the Nb/P ratio of 3/4. Furthermore, the ion-exchange and fluorescent properties of 1 have been studied.A two-dimensional niobium fluorophosphate (NH4)2(Nb3P4O19F3)(H2en)2·H2O with new Nb/P ratio (3/4) has been synthesized hydrothermally and characterized. The compound contains a novel two-dimensional 4.8-net layer constructed from the strict alternation of 4-connected NbO5F octahedra and 3-connected PO4 tetrahedra.Display Omitted►A two-step hydrothermal method. ►New Nb/P ratio (Nb/P = 3/4). ►(4, 3)-connected niobium fluorophosphate with 4.8-net layer. ►Two types of interesting NbO5F octahedra. ►Ion-exchange and fluorescent properties.
Keywords: Niobium fluorophosphate; 4.8-net; NbO5F octahedron; Ion-exchange; Fluorescence;

An efficient bonding-type Eu-containing copolymer as red phosphor applied in LED by Haigang Yan; Huihui Wang; Pei He; Jianxin Shi; Menglian Gong (1065-1068).
A luminescent europium-containing copolymer, poly(MMA- UA -co-Eu (DBM)2 (TOPO)2)was synthesized The copolymer was characterized by FT-IR, UV–vis, gel permeation chromatograph (GPC), ICP, thermogravimetric analysis (TGA), derivative thermal gravimetric analysis (DTG) and differential scanning calorimetry (DSC). The Eu-copolymer phosphor exhibited high thermal stability, high glass transition, excellent photoluminescence properties (PL), appropriate CIE chromaticity coordinates for red and good quantum yield (18%) under near-UV light excitation. An intense red-emitting light-emitting diode (LED) was fabricated by combining poly[UA-MMA-co-Eu (DBM)2(TOPO)2] with a 395 nm-emitting InGaN chip. The results indicate that the Eu-copolymer phosphor may act as a red component for fabrication of white LEDs.► Poly (UA-MMA) was prepared by reversed emulsion polymerization, methodology is simple, and shows big yield. ► The synthesis routines of copolymer poly(MMA-UA-co-Eu(DBM)2 (TOPO)2) as outlined in Fig. 1 is very convenient. ► The Eu-copolymer phosphor exhibited high thermal stability, high glass transition, excellent photoluminescence properties (PL), appropriate CIE chromaticity coordinates for red and good quantum yield (18%) under near-UV light excitation. ► The Eu-copolymer phosphor may act as a red component for fabrication of white LEDs.
Keywords: Eu-containing copolymer; Phosphor; Luminescence; LED;

Reactions of 25,26,27,28-tetrahydroxy-calix[4]arene (1) with 4 equiv. of m-carboxybenzenediazonium chloride in the presence of NaOAc∙3H2O in DMF produced a new azo calix[4]arene [H4L] (2) (H4L = 5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene) in 96% yield. Hydrothermal reactions of Cd(NO3)2·4H2O with H4L at 90 °C under pH = 5.0–6.0 gave rise to a coordination polymer {[H3O]2[Cd7L4(DMF)4(EtOH)2(H2O)2]·5DMF·11.5EtOH·H2O}n (3). Compound 3 was characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compound 3 consists of a 3D framework with an unprecedented (3346526371)(364135861) topology. The thermal properties of 2 and 3 were also investigated.A novel 3D coordination polymer {[H3O]2[Cd7L4(DMF)4(EtOH)2(H2O)2]·5DMF·11.5EtOH·H2O}n (3) {H4L = 5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene} was synthesized by reactions of Cd(NO3)2·4H2O and H4L under the solvothermal conditions. The molecular structure of 3 was characterized by elemental analysis, IR, and X-ray crystallography and its thermal property was investigated.Display Omitted► Reaction of Cd(NO3)2, cali[4]arene tetracaboxylic acid in DMF gave compound 3. ► Compound 3 is a 3D coordination polymer. ► Compound 3 has an unprecedented (3346526371)(364135861) topology.
Keywords: Cadmium; Solvothermal synthesis; Tetrakis(m-carboxyphenyl)azo calix[4]arene; Thermal properties; Coordination polymer;