Xintao Wu

Structural Diversity of Infinite 3d―4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

The syntheses, structures, and characterization of six Ln(3+)-Cu(2+)-glycine (Hgly) coordination polymers are described in this paper. They represent three types of structures. Type I (Ln=La (1), Pr (2), and Sm (3)) is a 1D catenarian polymer comprising [Ln(2)] nodes bridged by four cis-Cu(gly)(2) linkers. Type II (Ln=Eu (4) and Dy (5)) is a 2D open framework with a 4(4)-net, composed of novel [Ln(6)Cu(22)] cluster nodes linked by trans-Cu(gly)(2) linkers. Furthermore, the inner structures of the [Ln(6)Cu(22)] nodes, and the connection mode between the nodes and linkers are slightly different for 4 and 5. Type III (Ln=Er (6)) is a 3D open framework with a novel 3(6)4(18)5(3)6 topology, made up of [Er(6)Cu(24)] cluster nodes and trans-Cu(gly)(2) linkers. The rich variety of the resulting structures owes itself mainly to the interselection between the dynamic control of metalloligands and cationic components. A transition from frequency dependence to frequency independence is observed in the field-induced magnetization lag for 1-3. The frequency dependence at low temperatures may come from the antiferromagnetic Cu--Cu interaction through the [Ln(2)] nodes, whereas the frequency independence may be due to the disappearance of the antiferromagnetic Cu--Cu interaction at high temperatures.

Synthesis and Characterization of a Series of Novel Heptanuclear Trigonal‐Prismatic Polyhedra with Different Edge‐Ligands

Five novel heptanuclear trigonal-prismatic polyhedra, Na4[PrNi6(Gly)9(mu 3-OH)3(H2O)6].(ClO4)7 (1), Na2[PrNi6(Gly)8(mu 3-OH)3(mu 2-OH2)-(H2O)6].(ClO4)6.(H2O)2 (2), Na[DyNi6(Gly)7(mu 3-OH)3(mu 2-OH2)2(H2O)6].(ClO4)6.H2O (3), [SmNi6(Gly)6-(mu 3-OH)3Cl3(H2O)6].Cl3.(H2O)9 (4), and [ErNi6(Gly)6(mu 3-OH)3Cl3(H2O)6].Cl3.(H2O)9 (5), were synthesized through self-assembly and characterized by X-ray structure analysis. Complex 1 crystallizes in the trigonal P3 space group (a = b = 18.1121(2), c = 11.987(0) A, and Z = 2). Complex 2 belongs to the triclinic P1 space group (a = 16.0145(3), b = 20.58650(10), c = 20.8452(3) A, alpha = 78.0590(10), beta = 67.9200(10), gamma = 68.1540(10) degrees, and Z = 4). Complex 3 belongs to the monoclinic P2(1)/m space group (a = 14.9863(3), b = 13.533, c = 15.6171(3) A, beta = 116.8970(10) degrees, and Z = 2). Complexes 4 and 5 are isomorphous (4: trigonal, P3; a = b = 11.8661(4), c = 18.2034(10) A, Z = 2; 5: a = b = 11.9001(5), c = 18.1229(11) A, Z = 2). A Ln3+ ion is in the center of the prism formed by six nickel atoms. It coordinates to nine oxygen atoms. Its coordination polyhedron may be best described as a tricapped trigonal prism. The five complexes all have a core of [LnNi6(Gly)6-(mu 3-OH)3(H2O)6]6+ and were obtained through the edge-ligand exchange of the three mu 2-OH2 ligands of [LnNi6(Gly)6-(mu 3-OH)3(H2O)6(mu 2-OH2)3]6+ partly or wholly by glycine or Cl-. Magnetic measurements reveal that 1 and 4 exhibit antiferromagnetic interaction, while 5 exhibits a ferromagnetic interaction.

Three New Structural Types of Mo/Ag/S Polymeric Complexes

Wavelike, zigzag, and helical polymers are formed by the reaction of [MoS4 ]2- , Ag2 S, and a complementary cation. The framework of the polymeric anions depends on the valence state of the latter. For example, the butterfly-type anionic chain shown in the picture is formed upon use of a divalent cation. There is a general tendency that a higher valence state of the cation will induce a more compact chain structure.

Synthesis and crystal structure of two new heterometallic thioantimonates(III) [Ni(pda)2]CuI4SbIII2S6 and [Ni(dien)2]CuISbIII3S6,

Two different dimensional inorganic–organic hybrid heterometallic sulfide, [Ni(pda)2]Cu4Sb2S6 (1) and [Ni(dien)2]CuSb3S6 (2) were obtained by using 1,2-propanediamine (pda) and diethylenetriamine (dien) as the ligand, respectively.

Self-assembly of luminescent Sn(IV)/Cu/S clusters using metal thiolates as metalloligands.

Through the use of (Bu4N)2[Sn3S4(edt)3] (edt=SCH2CH2S(2-)) and Sn(SPh)4 as metalloligands, three neutral compounds have been obtained: [(Ph3P) 2Cu] 2SnS(edt)(2).2CH2Cl2.H2O (1a), [(Ph3P) 2Cu]2SnS(edt)2.2DMF.H2O (1b), and [(Ph3P)Cu] 2Sn(SPh)(6).3H 2O (2). Single-crystal X-ray diffraction studies revealed that compounds 1a and 1b contain the same neutral butterfly-like [(Ph3P)2Cu]2SnS(edt)2 cluster, which consists of one central SnS 5 dreich trigonal bipyramid sharing one vertex and two sides with two slightly distorted CuS 2P2 tetrahedrons. Compound 2 has a linear [(Ph3P)Cu]2Sn(SPh)6 cluster that is composed of a central distorted SnS 6 octahedron sharing two opposite planes with two slightly distorted CuS 3P tetrahedrons. Compound 1a exhibited an emission at 568 nm (tau=12.86 micros) in the solid state, while in CH 2Cl 2 solution, 1a exhibited a green emission at 534 nm (tau=4.75 micros). Compound 2 showed an intense red emission at 696 nm (tau=3.64 micros) upon excitation at 307 nm in the solid state.

The synthesis and characterization of a novel cubane-like cluster [(CH3CH2)4N]4 [{W2Cu2S4}(SCN)8]

A new synthetic procedure of the [(CH 3 CH 2 ) 4 N] 2 [W 2 S 4 (S 4 ) 2 ] compound under mild conditions is described and a novel heterometallic cubane-like cluster [(CH 3 CH 2 ) 4 N] 4 [{W 2 Cu 2 S 4 }(SCN) 8 ] has been synthesized by reaction of [(CH 3 CH 2 ) 4 N] 2 [W 2 S 4 (S 4 ) 2 ] with CuCl and KSCN. W 2 Cu 2 S 12 N 12 C 40 H 80 crystallizes in the monoclinic space group P 2 1 / c (No. 14) with cell parameters a =19.88(1), b =13.765(6), c =25.85(1) A, β=109.45(4)°, V =6669(6) A 3 ; Z =4; D calc =l.60 g cm −3 ; μ45.42 cm −1 ; T =296 K; M r =1608.66. Final R =0.057 for 4295 observed reflections with 1 >3σ( I ) and 453 variables. The unit cell contains four discrete high negative anions and sixteen discrete cations. The discrete anion comprises one cubane-like cluster core {W 2 Cu 2 S 4 } 4+ , six SCN − ligands attached to two W atoms and two SCN − ligands attached to two Cu atoms. The bond length of the WW bond and the two WCu bonds are 2.845(2) and av. 2.781(3) A, respectively. The W 2 S 4 moiety of {W 2 S 4 (S 4 ) 2 } 2− remains in the product, except the WS double bond lengths elongate slightly to av. 2.226(6) A.

Synthesis and circular dichroism spectra of silver(I) complexes with R,R-DIOP (4R,5R-trans-4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyl-1,3-dioxalane): crystal structures of [AgCl(R,R-DIOP)]2·2CHCl3, {[AgBr(R,R-DIOP)]2}2·CH2Cl2·2H2O, [AgI(R,R-DIOP)]2 and [AgSCN(R,R-DIOP)]2

The title silver(I) complexes as [AgX(R.R-DIOP)](2) dimers (X = Cl, Br, I or SCN) were synthesized either by the reaction of [Ag(NO3)(R,R-DIOP)](n) with NaX or the reaction of AgX with R,R-DIOP. The complexes were confirmed by elemental analysis, IR, H-1- and P-31-NMR, UV-vis and circular dichroism (CD) spectra, as well as single-crystal X-ray characterization, X-ray analysis showed that the silver atoms are tetrahedral, surrounded by two bridged halides and two phosphorus atoms of the bridged R,R-DIOP ligands. The Ag . . . Ag distances, ranging from 3.065(6) to 3.724(1) Angstrom, are dependent on the polarizability of the halide anions. All of the solid-state structures of the complexes are crystallized in triclinic, space group P1 (no. 1). The CD spectra of these complexes demonstrate their chiratity, and their Cotton effects vary according to the different halides, i.e. a negative band (at 241 nm) for 1 (X = Cl), a positive one for 2 (X = Br) and 3 (X = 1), and a strong positive band for 4 (X = SCN)

Controlled assembly and modification of inorganic systems

Qisheng Lin, John D. Corbett: A Chemical Approach to the Discovery of Quasicrystals and Their Approximant Crystals.- Andrew P. Grosvenor, Ronald G. Cavell, Arthur Mar: Bonding and Electronic Structure of Phosphides, Arsenides, and Antimonides by X-ray Photoelectron and Absorption Spectroscopies.- Zhong-Ning Chen, Feng-Rong Dai: Oxo-centered Triruthenium-acetate Cluster Complexes Derived from Axial or Bridging Ligand Substitution.- Zhonghai Ni, Renjie Li, Jianzhuang Jiang: New Progress in Monomeric Phthalocyanines Chemistry: Synthesis, Crystal Structures and Properties.- Sheng-Chang Xiang, Sheng-Min Hu, Tian-Lu Sheng, Ling Chen, and Xin-Tao Wu: Controllable Assembly, Structures and Properties of Lanthanide-Transition Metal-Amino Acid Clusters.

The first heterotrinuclear Pd-Cu cluster with two μ3-S bridging atoms synthesis and structure of [Pd2(PPh3)4(μ3-S)2(CuPPh3)]2(W6O19)

Abstract The compound [Pd2CuS2(PPh3)5]2(W6O19) was prepared from the reaction of Pd(PPh3)4 and WCu2(PPh3)3OS3 in air. The structure of the [Pd2(PPh3)4(μ3-S)2(CuPPh3)]2(W6O19) has been investigated by single crystal X-ray analysis. The cation is a heterotrinuclear Pd2Cu cluster bridged by two μ3-S atoms. Metal-metal interaction has been presented between copper and palladium atoms. The Pd(1)Cu and Pd(2)Cu distances are 2.789(3) and 2.889(2) A, respectively.