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Synthesis, Conformation and Character of W/Cu/S Supermolecule Clusters Containing Tp~* Group

Author: LvXue
Tutor: LangJianPing
School: Suzhou University
Course: Inorganic Chemistry
Keywords: Mo (W) / Cu / S clusters Tp ~ * Third-order nonlinear optical properties Crystal structure Ligand assembly
CLC: O611.4
Type: Master's thesis
Year: 2011
Downloads: 2
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Abstract


Mo (W) / Cu / S atomic clusters because its structure is rich and diverse, with a wide range of applications in materials science, industrial catalysis and life science has always been widespread concern of chemists and materials scientists. Previously reported Mo (W) / Cu / S of clusters most starting materials [AMO (W) S 3 ] (A = O, S, and Cp * ) and Cu (Ⅰ) compound obtained. In recent years, a new class containing TP * (Tp of * = (3,5 - dimethyl-pyrazol) hydrogen together borate) unit Mo (W) / Cu / S cluster precursors has better solubility and steric effects gradually attracted people's attention. Order to enrich such clusters and to look for better third-order nonlinear optical properties of the material, this thesis to [Tp * WS 3 ] - as cluster precursors expand research, the work is divided into the following two parts: 1) select [Et 4 N] [Tp * WS 3 ] (1) as the starting material and the Cu (I) compound to give a 5 having a different cluster core structure containing the TP * of W / Cu / S-clusters ; 2) opening cubane clusters configuration [Et 4 N] [Tp * of WS 3 (CuBr) 3 ] (2) as a precursor reaction and three nitrogen-containing organic ligand, to obtain a 4-containing cluster compounds having a different structure. Containing 2 Cluster Supramolecular. The main results are summarized as follows: First, the [Et 4 N] [Tp * WS 3 ] (1) and CuI, CuNCS and Cu ( CH 3 CN) 4 ClO 4 assembly heteronuclear metal clusters: [Et 4 N] [Tp * W (μ-S) 2 OCuCl] (3), [Et 4 N] [Tp * W (μ2-S) 3 (CuI) 2 ] · CH 2 Cl 2 (4), [Et 4 N] [Tp * W (μ 3 -S) 3 (CuI ) 3 ] (5), [Tp * W (μ2-S) 2 3 -S ) Cu (μ2-SCN) (CuCH 3 CN)] 2 (6), [{Tp * W (μ 3 -S) 3 Cu 3 (CH 3 CN) 3 } 2 < / sub> (μ6-Cl)] (ClO 4 ) 2 (7). Wherein the compound (3) [11] of the ring the MCU-configuration product, Compound (4) [12] of the butterfly MCU 2 - configuration of the product, compound (5) [13] in the opening cubane MCu 3 - configuration of the product, compound (6) [12] Shuangdie type MCU product of 2 - configuration, compounds (7) [13] double closed cubane MCu 3 - configuration product. Second, the opening cubane configuration [Et 4 N] [Tp * W (the μ 3 -S) 3 < / sub> (CuBr) 3 ] (2) as a precursor and three different types of nitrogen-containing ligands (including monodentate ligands α-MePy bidentate ligand 1,4-pyz and tridentate ligand MA) reaction, separation 4 containing cluster compounds with different structure types: the [Tp * W (the μ 3 -S) < sub> 3 Cu 3 (α-MePy) 3 3 -Br)] (PF 6 < / sub>) · 0.5CH 2 Cl 2 (8.0 .5 CH 2 Cl 2 ), {[ Tp * W (μ 3 -S) 3 Cu 3 (1,4-pyz) {(1 ,4-pyz) 0.5 } 2 3 -Br)] [Tp * WS 3 (CuBr) 3 ]} n (9), {[Tp * W (μ 3 -S) 3 Cu 3 Br (μ 3 -Br) 2 (MA) 2 ] · 2CH 3 OH} n (10.2 CH 3 OH), {[Tp * WS 3 Cu 3 Br (μ 3 -Br) (MA) 2 ] · CH 3 CN · 0.5Et 2 O} (11 · CH 3 CN · 0.5Et 2 O). Which compounds 8.0 .5 CH 2 Cl 2 and 11 · CH 3 CN 0.5Et 2 O is [Et 4 N] [Tp * W (μ 3 -S) 3 (CuBr) 3 ] ligand ratio of 1:3 and 1:2 of the monomeric structure; the cation of the compound 9 as a one-dimensional Z-type chain structure, the same as the cluster structure of the anion and the anion of the raw material 2; while compound 10.2 CH 3 OH neutral one-dimensional spiral containing clusters of supramolecular compounds. Electrospray ionization mass spectrometry characterization and third-order nonlinear optical properties of test compounds 8-11, because the resulting clusters in DMF solution exists mostly after the reorganization of the part of the fragment or fragments of fragments, so measured little difference between the third-order nonlinear optical properties.

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CLC: > Mathematical sciences and chemical > Chemistry > Inorganic Chemistry > Chemical elements and inorganic compounds > Inorganic synthetic chemistry
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