School of Chemistry & CRANN, University of Dublin, Trinity College, Dublin 2, Ireland.
Dalton Trans. 2012 Mar 14;41(10):2918-26. doi: 10.1039/c2dt11153e. Epub 2012 Jan 23.
Herein we report the intra- and inter-molecular assembly of a {V(5)O(9)} subunit. This mixed-valent structural motif can be stabilised as V(5)O(9)(L(1-3))(4) (1-3) by a range of organoarsonate ligands (L(1)-L(3)) whose secondary functionalities influence its packing arrangement within the crystal structures. Variation of the reaction conditions results in the dodecanuclear cage structure V(12)O(14)(OH)(4)(L(1))(10) (4) where two modified convex building units are linked via two dimeric {O(4)V(IV)(OH)(2)V(IV)O(4)} moieties. Bi-functional phosphonate ligands, L(4)-L(6) allow the intramolecular connectivity of the {V(5)O(9)} subunit to give hybrid capsules V(10)O(18)(L(4-6))(4) (5-7). The dimensions of the electrophilic cavities of the capsular entities are determined by the incorporated ligand type. Mass spectrometry experiments confirm the stability of the complexes in solution. We investigate and model the temperature-dependent magnetic properties of representative complexes 1, 4, 6 and 7 and provide preliminary cell-viability studies of three different cancer cell lines with respect to Na(8)H(2)[6]·36H(2)O and Na(8)H(2)[7]·2DMF·29H(2)O.
在这里，我们报告了一个 {V(5)O(9)} 亚基的分子内和分子间组装。这种混合价结构基元可以通过一系列有机胂酸盐配体 (L(1)-L(3)) 稳定下来，这些配体的二级官能团影响其在晶体结构中的堆积排列。反应条件的变化导致十二核笼状结构 V(12)O(14)(OH)(4)(L(1))(10) (4) 的形成，其中两个经过修饰的凸形建筑单元通过两个二聚体 {O(4)V(IV)(OH)(2)V(IV)O(4)} 部分连接。双功能膦酸配体 L(4)-L(6) 允许 {V(5)O(9)} 亚基的分子内连接，得到混合胶囊 V(10)O(18)(L(4-6))(4) (5-7)。胶囊实体的亲电空腔的尺寸由所包含的配体类型决定。质谱实验证实了复合物在溶液中的稳定性。我们研究并模拟了代表性配合物 1、4、6 和 7 的温度依赖性磁性质，并针对三种不同的癌细胞系进行了 Na(8)H(2)[6]·36H(2)O 和 Na(8)H(2)[7]·2DMF·29H(2)O 的初步细胞活力研究。
