中文摘要
以M6O198?(M=Nb, Ta)为原料,通过控制反应体系条件,合成新型[Nb7O22]9?阴离子;采用阳离子取代的方法,使M6O198? 阴离子与设定的目标阳离子反应, 制备具有新型结构的铌、钽多金属氧簇化合物;再以多金属氧簇阴离子作为多齿配体与碱土金属、过渡金属及稀土元素反应配位并引入有机配体,制备具有一维链状、二维层状及三维网状结构的以铌、钽多金属氧簇阴离子为基块的配位聚合物。探索铌、钽多金属氧簇阴离子与金属阳离子和有机配体共聚反应的条件,测定所得化合物的结构,研究化合物的氧化还原性质、热稳定性、导电性、非线性光学性质及光限幅特性,考察该类化合物组成、结构与性质之间的相关性。以丰富人们对铌、钽多金属氧簇化合物的认知,并为该类化合物走向实际应用提供技术储备。具有重要的理论意义和实际意义。。
英文摘要
The synthesis of polyoxoniobates remain a great challenge for synthetic chemists due to the inert activity of niobium species..Under the financial support of the Natural Science Foundation of China, we launched the study and exploitation on polyoxoniobates. Our work in this filed including: (1) We discovered the method for preparation of active Nb2O5, which can participate in the reaction directly; (2) Using the large cations instead of simple k+ and Na+ alkali metals ions, we obtained a novel giant wheel-shaped polyniobate cluster [{H2Nb6O19}?{[({KNb24O72H10.25}{Cu(en)2})2{Cu3(en)3(H2O)3}{Na1.5Cu1.5(H2O)8{Cu(en) 2}4 6}]24- and a giant cube-shaped polyniobate cluster [H23NaO8Cu24(Nb7O22)8]16-; (3) By the diffusion strategy, we synthesized two novel copper-undecaniobate clusters {[Cu(H2O)L]2Cu[Nb11O35H4]}5- (L = phen, 2,2′-bipy) and three 2D polyoxoniobates; (4) We explored the right condition and impact factor during the synthese course for the above compounds, studied the magnetic property and bioactivity of partial compounds..The successful synthese of these polyoxoniobates has important scientific significance in synthese chemistry, it will not only enrich the structural diversity of polyniobates, but also provide us an enlightening synthetic strategy for new polyoxoniobates.
结题摘要
由于铌的化学惰性,聚铌氧簇的合成一直是国际性的难题。在基金的资助下,本项目开展了活性五氧化二铌的制备研究,获得了制备可以直接参与反应的活性五氧化二铌的方法;采用大阳离子取代的方法,合成出了含有新颖巨型轮状阴离子和立方型阴离子的分子组成为 [{Nb6O19}8- {[({KNb24O72H9}-{Cu(en)2})2 {Cu3(en)3(H2O)3} {Na1.5Cu1.5 (H2O)8}Cu(en)2}4]6}33-]41- 和(K12Na4H23[NaO8Cu24(Nb7O22)8]o106H2O的聚铌氧簇;采用扩散-反应-结晶的试管合成方法,制备了组成为{[Cu(H2O)L]2Cu[Nb11O35H4]}5- (L = phen, 2,2′-bipy)的新型铌氧簇阴离子和具有一维和二维结构的铌氧簇配位聚合物;探索了该类化合物的生成条件和影响因素,对化合物进行了详细的结构表征,研究了所制备化合物的磁性和部分化合物的生物活性,将为聚铌氧簇的合成提供新的思想方法和合成策略,具有重要的科学意义。
