钌（Ⅱ）、铬（Ⅲ）配离子-多金属氧酸盐分子基化合物的合成及表征

【作者】 包冬梅；

【导师】 胡式贤； 由万胜；

【作者基本信息】 辽宁师范大学 ， 有机化学， 2003， 硕士

【摘要】 多酸分子基化合物由于具有优良的光、电、磁等的物理性质及结构，日益受到人们的重视，已成为热点的研究领域之一。 本文首次合成了5种联吡啶钌（Ⅱ）-Keggin结构和2种联吡啶钌（Ⅱ）-Dawson结构多酸分子基化合物，[Ru（bipy）₃]₂[SiW₁₂O₄₀]·2C₂H₅OH·8H₂O（1）、[Ru（bipy）₃]₂[GeW₁₂O₄₀]·4C₂H₅OH·4H₂O（2）、[Ru（bipy）₃]_1.5[PW₁₂O₄₀]·12H₂O（3）、[Ru（bipy）₃]_1.5[PMo₁₂O₄₀]·13H₂O（4）、[Ru（bipy）₃]_2.5[BW₁₂O₄₀]·8H₂O（5）、[Ru（bipy）₃]₃[P₂W₁₈O₆₂]·10H₂O（6）、[Ru（bipy）₃]₃[P₂Mo₁₈O₆₂]·8H₂O（7）。通过元素分析、IR光谱、UV-Vis光谱、¹H NMR谱、热重分析对所合成化合物进行表征，确定了化合物的组成和结构。UV-Vis光谱表明它们在可见光区有较强的吸收，其吸收端起始于750nm附近，可望成为优良的光催化剂。 首次合成了2种钌的三取代Keggin结构杂多钨酸衍生物，K₆H SiW₉Ru₃O₄₀·10H₂O（1）、K₆HGeW₉Ru₃O₄₀·12H₂O（2）。并通过元素分析、IR光谱、UV-Vis光谱、¹⁸³W NMR谱、热重分析对所合成的配合物进行表征，确定了化合物的组成和结构。UV-Vis光谱表明它们在紫外区200nm和260nm处的吸收带被指认为杂多阴离子的O_d→W和O_d／O_c→W荷移跃迁；在400-490nm产生的弱吸收带是由Ru³⁺的¹T_2g→¹Ag的跃迁引起的。化合物的¹⁸³W NMR谱表明多酸阴离子[XW₉O₃₄]^10-具有C_3v对称性。 首次合成了K₃[Cr₃O（OOCH）₆（H₂O）₃][α-GeW₁₂O₄₀]·12H₂O多酸分子基化合物，并通过元素分析、IR光谱、热重分析和X-射线衍射对所合成的化合物进行表征。X-射线单晶衍射确定了晶体结构，化合物中包含K₃[Cr₃O（OOCH）₆（H₂O）₃]⁺和α-Keggin结构GeW₁₂O₄₀^4-阴离子，结构解析表明化合物沿c轴方向整齐的重叠排列。X-射线粉末衍射在较低的2θ角处有最强的衍射峰，这是孔道结构化合物的结构特征，说明化合物具有微孔结构。用X-粉末衍射对晶体进行脱水和吸水实验，其结果表明该化合物为一透气型离子结晶，能够在干燥条件下失去水分子，在潮湿条件下吸附水分子，而本身分子结构不发生变化。更多还原

【Abstract】 Polyoxometalate molecule-based compounds are becoming interesting due to their unique structure and physical properties in photochemistry, electronics and magnetics.Tribipyridineruthenium-polyoxometalate with Keggin and Dawson structure molecule-based compounds, [Ru(bipy)3]2[SiWi2O40] 2C2H5OH 8H2O(1), [Ru(bipy)3]2 [GeW12O40] 4C2H5OH 4H2O(2) [Ru(bipy)3]15[PW12O40] 12H2O(3).[Ru(bipy)3]1.5[PMo12O40] 13H2O (4) , [Ru(bipy)3]2.5[BW12O40] 8H2O(5), [Ru(bipy)3]3[p2W18O62] 10H2O(6) , [Ru(bipy)3]3[P2Mo18O62] 8H2O(7), were synthesized and characterized by elemental analysis, IR spetra, UV-Vis spetra, 1H NMR spetra and TG. UV-vis showed strong absorption in visible region for the complexes, the offset of which is at 750nm. They may be becoming excellent photocatalysts.Ruthenium-substituted trivacant Keggin-type heteropolytungstes, K6H SiW9Ru3O40 10H20 (1), K6HGeW9Ru3O40 12H2O(2), were characterized by elemental analysis, IR spetra, UV-Vis spetra, 183W NMR spetra and TG. UV-vis showed strong absorption in visible region for the complexes, and 183W NMR spectra indicate that the polyoxometalate anions possess C3v Symmetry.A polyoxometalate molecule-based compound, K3[Cr3O(OOCH)6(H2O)3][ a -GeW12O40]-12H2O, were synthesized and characterized by elemental analysis, IR spetra, TG and X-ray diffration. X-ray single crystal diffration shows Cr3O(OOCH)6(H2O)3+ cations and GeWi2O404-anions were arranged over lapping along c axes. X-ray powder diffration pattern of the compound shows well resolved patterns with a prominent peak at low 2 0 , confirming that it had porous structure. By mean of dehydration and adsorption of water experiments, it is found thatn it is porous ion crystal, and is able to adsorb small molecules such as water molecules selectively.更多还原