Shao-Fang Lu

A novel left-handed double helicate constructed from l-tartrate bridged molybdenum(vi) and gadolinium(iii) atomsElectronic supplementary information (ESI) available: crystallographic data, TGA, powder X-ray patterns, ORTEP structure and molar susceptibility plot for compound 1. See http://www.rsc.org/suppdata/cc/b3/b301542d/

The one-dimensional double helicate, [NH4][Mo2O4Gd(H2O)6(L-C4H2O6)2] x 4H2O (1), which was synthesized by the reaction of GdCl3, L-tartaric acid and ammonium molybdate in acidified water solution, is built up by two heft-handed single-helical chains, linked up further by eight-coordinated GdIII pieces in an enantiopure left-handed double helical configuration, of which each helix is formed by L-tartrate bridged six-coordinated MoVI atoms.

Synthesis and Structural Characterization of the Novel Cluster Compound {[Mo3S7(dtp)3]4⋅I}{(HgI3)3}⋅4 H2O (dtp=S2P(OC2H5)2−)

Reaction of [Mo3Y(μ-S)3(dtp)4(H2O)] (Y=O, S; dtp=S2P(OC2H5)2−) with HgI2 gave the novel compound {[Mo3S7(dtp)3]4⋅I}{(HgI3)3}⋅4 H2O (1), which contains a {[Mo3S7(dtp)3]4⋅I} tetramer and (HgI3)−. Compound 1 has been characterized by IR, Raman, UV/Vis, and NMR spectroscopy and single-crystal X-ray diffraction analysis. It is shown that this formation process can be referred to as a new cluster reaction. The structure and spectroscopic data of the tetramer is also compared with that of the related discrete cluster [Mo3S7(dtp)3⋅I]. Crystal data: space group F23, a=26.786(3) A, V=19218.7(4) A3, Z=4, R=0.059.

Synthesis and structural characterization of hybrid Group 12, 14, 15 metals-molybdenum (tungsten) cluster compounds

For the heterometallic cluster compounds containing a core of [M3YS3M] (4 + n)+ (M= Mo, W; Y= O, S; M= metal atom except Mo, W), a relatively comprehensive understanding has already been made when M n + appears to be a transition metal. When M n + is a main group metal, however, what will be the situation? This certainly arouses the interest among the chemists. In this present work, the synthesis, new reaction types, crystal structures and spectroscopic characterization of a series of 33 hybrid Mo(W)–Group 12, 14, 15 metal clusters are summarized. These crystals can be put into three categories, i.e. the single cubane type which contains a [M3YS3M ]c ore (M=Mo, W; Y= O, S; M= Sn, Pb, Sb, Bi) (SC type), the double cubane clusters coupled by two bridging oxygen atoms possessing a [Mo3OS3M (-O)]2 core (M= Pb, Bi) (DC type) and the ionic clusters (IO type) which consists of a {Mo3} cluster cation and a M complex anion (M= Cd, Hg). It is shown that the incorporation of the main group metal M is through MS bonding between M and three (-S) atoms of the [M3YS3] cluster core, similar to the case when M is a transition metal atom. The bonding is however comparatively looser than in the case of a transition metal. The synthetic reactions and structural features of these clusters are discussed. Furthermore, information on the third-order nonlinear optical property observed in some of these compounds is reported.

Synthesis, structures and properties of a series of novel left- and right-handed metal coordination double helicates with chiral channels

The reactions of LnCl3 (Ln = lanthanide cations), L- or D-tartaric acid and molybdate in acidified aqueous solutions gave rise to the enantiopure left- or right-handed double helical coordination metal compounds, {A[Mo2VIO4LnIII(H2O)6(C4H2O6)2]·4H2O}n (Ln = Sm, Eu, Gd, Ho, Yb, Y; C4H2O6 = L- or D-tartaric acid; A = NH4 or H3O; MoLn represent all complexes), which have been characterized by single X-ray crystal structure analyses, IR, FT-Raman, TGA, XRPD, electric conductivity, EPR and magnetic susceptibility studies. The TGA and XRPD studies for compound MoGd suggest that the backbone is “collapsed” with the removement of aqua ligands and crystallization water molecules. However, it is easily reverted to the original compound after being immersed in water, as confirmed by similar XRPD patterns. The electric conductivity studies for these compounds reveal they are semiconductors. As aforementioned, the conductivity behaviors for the dry sample and reversed sample of MoGd are also very similar, in line with the XPRD results. Study of the magnetic susceptibilities reveal that the magnetic behaviors for MoGd, MoDy, MoHo and MoYb obey the Curie–Weiss law.

Synthesis, crystal structure and bonding features of a trinuclear cluster [Mo3X(S2)3(dtp)3I3] (X=O,S) with layer-like packing

Abstract The reaction of Mo 3 OS 3 (dtp) 4 (H 2 O) (dtp=S 2 P(OC 2 H 5 ) 2 ) with CuI yielded the new trimolybdenum cluster [Mo 3 (μ 3 -X)(μ 2 -S 2 ) 3 (dtp) 3 I 3 ] (X=58%O+42%S). Crystal structure analysis showed that the compound has a [Mo 3 X(S 2 ) 3 ] 4+ cluster core, and the I 3 − group functions as a two-way coordinated ligand which links the three out-of-{Mo 3 } plane S atoms in the cluster core at one end (I–S∼3.3 A) and two adjacent trinuclear clusters at the other (I⋯S∼3.6 A), thus forming a [Mo 3 X(S 2 ) 3 ] cluster layer. The bonding features of the cluster characteristic of a semiconductor are demonstrated by energy band and density functional calculations.

The synthesis and structural characterization of a novel Bi–Mo double cubane cluster coupled by two bridging oxygen atoms { [Mo3 (BiI3)OS3 (μ-OAc)2 (py)3]2 (μ-O)2}·2 (H2O)

Abstract With [Mo3 (μ3-O) (μ-S)3 (μ-OAc)2 (dtp)2 (py)] (dtp=S2P(OC2H5)2)−; OAc=OOCCH −3; py=C5H5N) as the starting material, the reaction together with BiI3 in presence of (H2O) results in a novel Bi–Mo double-cubane cluster coupled by two bridging oxygen atoms { [Mo3 (BiI3) (μ3-O) (μ3-S)3 (μ-OAc)2 (py)3]2 (μ-O)2}·2 (H2O) 2. The cluster 2 has been characterized by IR, Raman, UV–Vis, NMR and single-crystal X-ray study. A comparison is made between these results and those of the previously reported single cubane Bi–Mo cluster [Mo3 (BiI3) (μ3-S)4 (μ-OAc) (dtp)3 (py)] 1.

Meta-barium borate, II-BaB2O4, at 163 and 293 K.

The single-crystal X-ray diffraction structure analysis of an excellent non-linear optical material, viz. II-BaB2O4 or Ba3(B3O6)2, has been carried out at 163 and 293 K. The two sets of structural data are compared and indicate a significant shortening of the c axial length in the unit cell at 163 K, whereas the a and b axial lengths essentially do not change.

Bis­(1-acetonyl­pyridinium) pyridinium hexa­iodobismuth(III)

The crystal structure of the title complex, (C(8)H(10)N)(2)(C(5)H(6)N)[BiI(6)], contains discrete [BiI(6)](3-) anions, and (HNC(5)H(5))(+) and (CH(3)COCH(2)NC(5)H(5))(+) cations separated by normal van der Waals contacts. The [BiI(6)](3-) anion has the Bi atom on an inversion centre. The (HNC(5)H(5))(+) cation also lies about an inversion centre and is disordered. The (CH(3)COCH(2)NC(5)H(5))(+) cation lies in a general position.