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Construction, Characterization and Properties of Tp~*-Containing W/S/Cu Clusters

Author: WeiLiPei
Tutor: LangJianPing;RenZhiGang
School: Suzhou University
Course: Inorganic Chemistry
Keywords: Tungsten / copper / sulfur clusters Double cubane Crystal structure Synthesis Third-order nonlinear optical properties
CLC: O611.4
Type: Master's thesis
Year: 2011
Downloads: 4
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Abstract


Mo (W) / Cu / S clusters due to their structural diversity and potential applications in the field of industrial catalysis and optoelectronic materials chemists and materials scientists and highly favored. At the same time, with the metal-sulfur clusters of double cubane structure because its structure is similar to the active center of nitrogenase iron-molybdenum factor FeMoco (MoFe7S9) and PN-cluster (Fe 8 S 9 ), has aroused widespread attention and study. How to become one of the hot cluster compounds with chemical synthesis of metal-sulfur clusters of double cubane structure. We select [Et 4 N] [Tp * WS 3 ] for the a starting material, and AgSCN reaction, synthesis associated with an S-S bond bridge double [Tp * WS 3 ] unit new W / S precursor [(Tp * WS 2 ) 2 (μ-S 2 < / sub>)]; with AgSCN and NaSCN reaction containing double W W / S precursor [Et 4 N] [Tp * W2S 2 (μ- S) the 2 (SCN) 2 ]; the select the dimeric precursor [(Tp * WS the 2 ) 2 (μ-S 2 )] with CuX (X = Cl, Br, I) by self-assembly, three double cubane structure of the neutral clusters; CuX in Et 4 NX (X = Cl, Br) self-assembly in the presence of two double cubane structure ionic clusters, and by elemental analysis, infrared and X-ray single crystal diffraction and other characterization, testing a part of the product of the mass spectrum and the third-order nonlinear optical properties. The main content of this paper is as follows: Mo (W) / S type and synthetic precursor of the method of synthesis of metal-sulfur clusters with double cubane structure are reviewed. Second, starting from [Et 4 N] [Tp * WS 3 ] (1) with two equivalents of AgSCN reaction in MeCN to give the neutral compound [(Tp * WS 2 ) 2 (μ-S 2 )] (2), the compound 2 dimeric structure can be regarded as two [ Tp * WS 2 W atoms in the unit through a μ-S 2 2 - connected; with AgSCN and NaSCN reaction generated ionic compounds containing double W [Et 4 N] [Tp * W2S 2 (μ-S) 2 (SCN) 2 ] ( 3), wherein the two W atoms are connected through two μ-S bridge. These two compounds can be used as a precursor with Cu salt self-assembly reaction. Third, the precursor is selected as the starting material with an excess of CuX (X = Cl, Br, I) in the MeCN and CH 2, Cl 2 or CHCl 3 a mixed solvent of self-assembly reaction is performed to obtain a three double cubane structure neutral W / Cu / S clusters [{Tp * W (μ3-S) 3 Cu 3 (μ-Cl)} 2 Cu (μ-Cl) 2 (μ7-Cl) (MeCN)] 2 (4), [{Tp * W (μ3-S) 3 Cu 3 } 2 Br (μ- the Br) 2 (μ4-Br) (MeCN)] (5) and [{Tp * W (μ3-S) 3 Cu 3 } 2 {Cu 2 (μ-I) 4 (μ3-I) 2 }] (6) . In addition, the 2 and CuX Et 4 NX (X = Cl, Br) under the existence of the self-assembly reaction generates two double cubane structure ionic W / Cu / S cluster compounds [Et 4 N] [{Tp * W (μ3-S) 3 Cu 3 X} 2 (μ-X) 2 (μ4-X)] (7: X = Cl; 8: X = Br). To cluster 4, two [Tp * W (μ3-S) 3 Cu 3 ] 2 divalent cations through a μ7 -Cl-bridge, two μ-Cl-bridge and a [Cu (MeCN) (μ-Cl) 2 ] bridge; in cluster compounds 5, 3 Cu [Tp * W (μ3-S) 3 (MeCN)] 2 and [Tp * W (μ3-S) 3 Cu 3 Br] connected through a μ4-Br-bridge and two μ-Br-bridge; in cluster compounds 6, two the [Tp × W (μ3-S) 3 Cu 3 ] 2 unit through a linear [(μ-I) Cu the (μ3-I) the 2 Cu (μ-I) 2 ] 4 cluster is connected to the nuclear unit; cluster compounds 7 and 8 two [Tp * W (μ3-S) 3 Cu 3 X] unit through a μ4-X-bridge and two μ-X- (X = Cl, Br) bridge. In addition, we use the four-wave mixing (DFWM) compounds 2,4-8 MeCN/CH2Cl2 mixed solution of the third-order nonlinear optical tests. Compounds 2,4-8 second-order nonlinear hyperpolarizability γ were 1.25 × 10 -31 esu (2), 3.12 × 10 -31 esu ( 4), 2.63 × 10 -31 esu (5), 2.77 × 10 -31 esu (6), 2.76 × 10 -31 esu (7) and 2.98 × 10 -31 esu (8). Compounds 4-8 second-order nonlinear hyperpolarizability γ value of compound 2 2.10 2 .49 times, and compound 2 γ value than compounds [Et 4 3 ] (of 1.07 × -32 esu), is 11.7 times greater.

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