The "Complex-in-a-Complex" cations [(acac)2M⊂RU6(p-iPrC6H4Me)6(tpt)2(dhbq)3]6+:: A Trojan horse for cancer cells
The "Complex-in-a-Complex" cations [(acac)2M⊂RU6(p-iPrC6H4Me)6(tpt)2(dhbq)3]6+:: A Trojan horse for cancer cells
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DOI：
10.1002/anie.200800186
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Dyson, Paul J.
中科院分区：
文献类型：
--
作者：
Therrien, Bruno;Suess-Fink, Georg;Dyson, Paul J.
直接合成用于组装分子纳米对象的有机金属笼形分子是化学研究的一个热点领域。[1]通过结合Stang[2]提出的“分子夹”策略和Fujita首创的“分子嵌板”策略，[3]我们最近合成了六个(η6-芳烃)Ru或(η5-五甲基环戊二烯)Ru单元由两个三角2，4，6-三(吡啶-4-基)-1，3，5-三嗪(TPT)板和三个二氯[4]或草醛[5]桥连接在一起的三角棱柱笼形分子。我们现在将这一原理推广到构造更大的阳离子六核金属配位体[Ru6(p-iPrC6H4Me)6(TPT)2-(Dhbq)3]6+(16+)，它包含了对伞花烃结构块，由2，5-二羟基-1，4-苯醌(Dhbq)(Dhbq)配体桥联，由两个TPT亚基连接(方案1)。以75%的产率分离得到阳离子络合物1-(OSO2CF3)6。在[Pd(Acac)2]或[Pt(Acac)2](acac=乙酰丙酮)存在下，也可以实现16+的组装，从而在不影响总收率的情况下得到[(Acac)2Pd&1]6+和[(Acac)2pt&1]6+。阳离子[(Acac)2Pd&1]6+和[(Acac)2pt&1]6+均为三氟盐。
The directed synthesis of organometallic cage molecules for the assembly of molecular nano-objects is a topical area of chemical research.[1] By combining the “molecular clip” strategy developed by Stang [2] with the “molecular paneling” strategy pioneered by Fujita,[3] we recently synthesized trigonal-prismatic cage molecules in which six (η6-arene) ruthenium or (η5-pentamethylcyclopentadienyl) rhodium units are held together by two trigonal 2, 4, 6-tris (pyridin-4-yl)-1, 3, 5-triazine (tpt) panels and three dichloro [4] or oxalato [5] bridges. We have now extended this principle to construct the larger cationic hexanuclear metalloprism [Ru6 (p-iPrC6H4Me) 6 (tpt) 2-(dhbq) 3] 6+(16+), which incorporates p-cymene ruthenium building blocks and is bridged by 2, 5-dihydroxy-1, 4-benzoquinonato (dhbq) ligands and connected by two tpt subunits (Scheme 1).The hexametallic cation 16+ was prepared from the dinuclear complex [Ru2 (p-iPrC6H4Me) 2 (dhbq) Cl2][6] and tpt in the presence of AgO3SCF3. The cationic complex was isolated and characterized as its triflate salt 1-(OSO2CF3) 6 in 75% yield. The assembly of 16+ can also be achieved in the presence of [Pd (acac) 2] or [Pt (acac) 2](acac= acetylacetonato) to give the “complex-in-a-complex” cations [(acac) 2Pd&1] 6+ and [(acac) 2Pt&1] 6+ without affecting the overall yield (Scheme 2). Cations [(acac) 2Pd&1] 6+ and [(acac) 2Pt&1] 6+ were both isolated as their triflate salts.