Hydrothermal Syntheses and Crystal Structures of Cobalt(Ⅱ) Complexes Constructed by Dipyrido[3,2-a:2',3'-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.

Synthesis,Structure and Photoluminescence of a Binuclear Zinc(Ⅱ) Coordination Polymer Based on 2-Carboxycinnamic Acid and Dipyrido[3,2-a:2′,3′-c]-phenazine

A binuclear zinc（Ⅱ） complex with 2-carboxycinnamic acid （2-ccm） and dipyrido- [3,2-a：2＇,3＇-c]phenazine （DPPZ）, {[Zn2（2-ccm）2（DPPZ）2]·2H2O}n, was synthesized and characterized by elemental analysis, IR, single-crystal X-ray diffraction, thermal gravimetry and fluo- rescent emission. It crystallizes in monoclinic, space group P21/c with a = 13.409（4）, b = 25.530（7）, c = 13.952（4） A, β = 99.554（3）°, V= 4710（2） A3, Z= 4, C56H36N8O10Zn2, Mr= 1111.67, Dc = 1.568 g/cm3, μ（MoKα） = 1.093 mm^-1, F（000） = 2272, R = 0.0422 and wR = 0.0895. In the crystal, the basic unit of 1 is a binuclear Zn2 entity which is linked by 2-ccm ligand to form a 1D double chain along the a axis. The O-H...O hydrogen bonding and π-π interactions lead to a 3D supramolecular motif. In addition, thermal and luminescent properties of complex 1 have also been investigated.

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a：2？,3？-c]phenazine and 2,4＇-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd（2,4＇-bpdc）（DPPZ）]2n·n H2O（1） and [Zn（2,4＇-Hbpdc）2（DPPZ）]· H2O（DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, 2,4＇-H2bpdc = 2,4＇-biphenyldicarboxylic acid） have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction（XRD） and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper(Ⅱ) Complex:[Cu_6(DPPZ)_4(btc)_4(H_2O)_8]·5H_2O

A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.

Synthesis, Crystal Structure and Luminescence of a New Two-dimensional Pb(Ⅱ) Coordination Polymer

A new two-dimensional Pb（Ⅱ） coordination polymer, [Pb2（L）（tpphz）1.5（NO3）2]·H2O（1）, has been obtained by the hydrothermal reaction of tetrapyrido[3,2-a：2′,3′-c：3′′,2′′-h：2′′′,3′′′-j]-phenazine（tpphz） and 2,2′-bipyridyl-3,3′-dicarboxylic acid（H2L）. It crystallizes in monoclinic, space group P21/c with a = 15.344（3）, b = 14.111（3）, c = 21.963（4） ？, β = 106.89（3）o, V = 4550.1（16） ？3, Z = 4, C48H26N13O11Pb2, Mr = 1375.20, Dc = 2.007 g/cm^3, F（000） = 2628, μ（Mo Ka） = 7.471 mm-1, R = 0.0339 and w R = 0.0808. In 1, the two crystallographically independent tpphz ligands adopt the same bis-chelating coordination mode, but they play different roles in the structure of 1. One type of tpphz ligands bridge the Pb（Ⅱ） cations to generate a zigzig chain, where the L anions are located on one side of the chain. Further, adjacent chains are linked by the other type of tpphz ligands into a two-dimensional layer structure. Additionally, the solid state luminescent property of 1 was also studied at room temperature.

A New Two-dimensional Cadmium(Ⅱ) Coordination Polymer Constructed by 1,10-Phenanthroline Derivative and Flexible Dicarboxylate:Syntheses,Structure,Thermal Behavior and Luminescence

In this work,a new two-dimensional Cd（Ⅱ） coordination polymer,[Cd3（L）2（cis-1,4-chdc）2（trans-1,4-chdc）]（1,L = 11-fluoro-dipyrido[3,2-a：2’,3‘-c]phenazine and 1,4-H2 chdc = 1,4-cyclohexanedicarboxylatic acid）,has been prepared under hydrothermal conditions.It crystallizes in triclinic,space group P1 with a = 8.6951（8）,b = 10.8362（9）,c = 14.9445（13） A,α = 76.443（2）,β = 81.8670（10）,γ = 82.0640（10）°,V = 1347.0（2） A^3,Z = 1,C60H48Cd3F2N8O12,Mr = 1448.26,Dc = 1.785 g/cm^3,F（000） = 722,μ（Mo Ka） = 1.255 mm^-1,R = 0.0333 and w R = 0.0790.The 1,4-chdc^2-carboxylates bridge the Cd（Ⅱ） cations to form a tri-nuclear Cd（Ⅱ） cluster,which are held together by the cis-1,4-chdc^2-ligands to generate a double-stranded chain.Further,the trans-1,4-chdc^2-ligands bridge adjacent double-stranded chains to yield an interesting two-dimensional network.The π-π interactions among L ligands of neighboring networks result in an interesting three-dimensional supramolecular architecture.In addition,the thermal behavior and luminescent property of 1 have been studied.

A New Porous Cadmium(Ⅱ) Complex Based on 1,10-Phenanthroline Derivative and Dicarboxylate:Syntheses, Structure, Thermal Behavior and Luminescence

A new porous Cd（Ⅱ） coordination compound, namely, [Cd（bpdc）（L）2]·3H2O（1, L = 11-fluoro-dipyrido[3,2-a：2,3-c]phenazine and bpdc = 1,1-biphenyl-2,2-dicarboxylate） was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffraction. It crystallizes in tetragonal, space group P4122 with a = 9.8486（4）, b = 9.8486（4）, c = 45.925（4）A, V = 4454.5（5） 3, Z = 4, C50H29 Cd F2N8O7, Mr = 1004.21, Dc = 1.497 g/cm^3, F（000） = 2028, μ（Mo Ka） = 0.562 mm^-1, R = 0.0566 and w R = 0.1585. Each Cd（Ⅱ） atom is coordinated by one bpdc anion and two L ligands to give a discrete molecule. Neighboring discrete molecules are stacked by π-π interactions among L ligands, resulting in an interesting 1D supramolecular chain. Moreover, the 1D supramolecular chains are packed with each other to give a porous structure, in which an infinite channel is filled with water molecules. In addition, the thermal behavior and luminescent property of 1 have also been studied.