Synthesis and Structure of a Dinuclear Copper（Ⅱ）- ditetrazolate Involving in situ Ligand Synthesis

The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuCl2, 2,2′-bipyridine and H2O affords a novel dinuclear copper(II)-ditetrazolate, [Cu(bpy)- (pdtz)]2 (Hpdtz = 5,5′-1,2-phenylene-ditetrazole, bpy = 2,2′-bipyridine). The pdtz ligand is generated in situ through Sharpless 2 3 cycloaddition reaction. Its crystal structure was deter- mined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P21/n with a = 8.2096(16), b = 18.580(4), c = 11.838(2) , β = 103.12(3)o, V = 1758.5(6) 3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm3, F(000) = 876 and μ = 1.272 mm-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.     

Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

Synthesis and Crystal Structure of a Heterometallic Trinuclear Ni/Ag/S Compound

A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I > 2σ(I).     

Co-crystallization of Resorcin[4]arene Tetracarboxylic Acid with Triethylamine: Synthesis and Crystal Structure

Treatment of resorcin[4]arene tetracarboxylic acid 1 with triethylamine in the presence of Co(CH3COO)2·4H2O and 4,4'-bipyridine gave a co-crystallization 14-·4Et3NH+(C32H20O164-·4Et3NH+,Mr=1069.27) from ethanol and water.The compound was structurally determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n,with a=8.1763(18),b=12.913(3),c=28.724(7) ,β=97.574(4)o,V=3006.3(12) 3,Z=2,Dc=1.181 g/cm3,F(000)=1152,Rint=0.0275,T=293(2) K,μ=0.086 mm-1,the final R=0.0634 and wR=0.1752 for 5082 observed reflections with Ⅰ 2σ(Ⅰ).The co-crystallization is very stable at room temperature.Possibly,a network of N-H···O(=C) plays an important role in the structure.Meanwhile,the compound emits a weak cyan luminescence with peak maximum band at 458 nm.     

Synthesis and Crystal Structure of a New Glycinato Copper Compound

1 INTRODUCTION Amino acids (AA) are some of the most important biological ligands, and metal ions are known to par- ticipate in a variety of biological reactions, therefore, research on the coordination behavior of metal-ami- no acid complexes is one of the most essential ele- ments of chemical biology[1, 2]. For over three deca- des their structures have been of considerable inte- rest and importance in coordination chemistry[2, 3]. Studies of these relatively simple complexes may en- ha…     

KCs2[Pb2Br5(HCOO)2]: A Polar 3D Lead-Bromide Framework Exhibiting Strong Second-Harmonic Generation Response

The discovery of new nonlinear optical (NLO) crystals with excellent properties is in urgently demand because of their ability to generate coherent light. Herein, we report an unique NLO lead bromide formate, KCs₂[Pb₂Br₅ (HCOO)₂], which has been synthesized by a mix-solvothermal method. KCs₂[Pb₂Br₅(HCOO)₂] exhibits strong phase-matching second-harmonic generation (SHG) response (6.5×KDP), large birefringence (0.16@ 1064 nm), and a wide transparent window in most visible light and mid-IR region. Interestingly, KCs₂[Pb₂Br₅(HCOO)₂] features a polar 3D lead-bromide framework in which adjacent Pb−Br layers containing coplanar Pb₆Br₆ rings are not only parallel to each other, but also orient in the same direction. These oriented arrangements are responsible for the strong SHG response and large birefringence that are elucidated by both local dipole moment and theoretical calculations. This research provides a new strategy to explore subsequent NLO crystals.     

Flexible porous coordination polymers constructed from 1,2-bis(4-pyridyl)hydrazine via solvothermal in situ reduction of 4,4'-azopyridine

Solvothermal reactions of Zn(NO(3))(2), 1,4-benzenedicarboxylic acid (H(2)bdc), and 4,4'-azopyridine (azpy) in different conditions yielded [Zn(bdc)(bphy)]·DMF·H(2)O (1a, bphy = 1,2-bis(4-pyridyl)hydrazine, DMF = N,N-dimethylformamide) and [Zn(bdc)(bphy)]·EtOH·H(2)O (1b) with two-fold interpenetrated dmp topology and [Zn(2)(bdc)(2)(bphy)]·1.5EtOH·H(2)O (2a) and [Zn(2)(bdc)(2)(bphy)]·DMA·1.5H(2)O (2b, DMA = N,N-dimethylacetamide) with two-fold interpenetrated pcu topology. The in situ reduction of azpy to bphy was confirmed by single-crystal structures and LC-MS analyses of the acid-digested crystalline samples, as well as controlled solvothermal experiments. Removal of the guest molecules in 1a/1b and 2a/2b converts the materials to guest-free phases [Zn(bdc)(bphy)] (1) and [Zn(2)(bdc)(2)(bphy)] (2), respectively, which were identified by PXRD. CO(2) sorption experiments performed at 195 and 298 K showed low porosity for 1 and gated sorption behavior for 2. At 298 K, 2 exhibits high selectivity for adsorbing CO(2) over CH(4).     

Syntheses, crystal structures, and characterization of As(III) and As(V) thioarsenates, [Mn2(phen)(As2S5)]n and [Mn3(phen)3(AsS4)2]n·nH2O

The hydrothermal reactions of As, Mn, S, phen (phen=1,10-phenanthroline), and en (en=ethylenediamine) yield two manganese As(III) and As(V) thioarsenates, [Mn₂(phen)(As^III₂S₅)]_n (1) and [Mn₃(phen)₃(As^VS₄)₂]_n·nH₂O (2), respectively. Single-crystal X-ray diffraction analyses reveal that compound 1 is a two-dimensional (2D) layer of (6,3) topology. The 18-membered rings within the 2D porous layers are formed by corner-, edge-, and face-sharing cubane-like [Mn₂As₂S₄] units along the [100] direction. Whereas compound 2 is a one-dimensional (1D) chain structure. They are both characterized by IR, elemental analysis, EDS, and X-ray powder diffraction. The thermogravimetric analysis of 1 and 2 are discussed. Both the compounds are semiconductors with the band gap of E_g (compound 1)=2.01 eV (617 nm) and E_g (compound 2)=1.97 eV (629 nm), respectively. In addition, the variable-temperature magnetic susceptibility data suggest weak antiferromagnetic interactions between the Mn²⁺ ions in these two compounds.     

Microporous Zinc Formate for Efficient Separation of Acetylene over Carbon Dioxide

Separation of acetylene(C₂H₂) from carbon dioxide(CO₂) by adsorbents is very challenging owing to their high similarity on molecular shape and dimension. Exploring inexpensive and easily available porous materials is of importance to facilitate the practical implementation of the challenging but energy-efficient separation. Herein, we utilize an easily available porous material[Zn₃(HCOO)₆] for the selective separation of C₂H₂ over CO₂. Because of the pore confinement in[Zn₃(HCOO)₆](pore size of 0.47 nm) and accessible oxygen sites for preferential binding of C₂H₂, this material exhibits high low-pressure uptake for C₂H₂(63 cm³/cm³ at 10 kPa and 298 K) and high C₂H₂/CO₂ selectivity(7.4 under ambient conditions) that is comparable to those of out-performing porous materials. The efficient separation of[Zn₃(HCOO)₆] for C₂H₂/CO₂ mixture has also been confirmed by the breakthrough experiments.     

Hydrothermal Syntheses and Characterizations of Two One-dimensional Molybdenum 1,4-Butylenediphosphonates

1 INTRODUCTION Interest in metal phosphonate chemistry has in- creased in recent years, not only because of their rich structural chemistry[1～3] but also owing to their potential applications in catalysis, absorption and intercalation reaction[4～6]. The introduction of a se- cond metal-ligand component as a charge-compen- sating unit and structure-directing component into polyoxomolybdenum/oxovanadium organodi-phos- phonates has provided us a powerful method to syn- thesize this family o…