Site-Specific Installation and Study of Electroactive Units in Every Layer of Dendrons
Site-Specific Installation and Study of Electroactive Units in Every Layer of Dendrons
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DOI：
10.1021/jo902109u
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发表时间：
2009-12-18
影响因子：
3.6
通讯作者：
Thayumanavan, S.
中科院分区：
文献类型：
--
作者：
Azagarsamy, Malar A.;Krishnamoorthy, Kothandam;Thayumanavan, S.
虽然在树枝状聚合物的核心处的官能团的封装是很好理解的，但是关于它们的中间层甚至外围知之甚少。在这里，我们报告油的每一层的树枝状聚合物的系统调查，将一个单一的二茂铁单元在明确的位置在树枝状。通过利用树枝状聚合物测序方法实现了二茂铁单元的位点特异性掺入。我们发现，在中间层的二茂铁的氧化还原电位值显着不同的核心和外围。虽然氧化还原电位值是位置依赖性的，非均相电子转移速率（k（0））没有显着变化，观察到相对于位置。这是由于树枝状大分子的自由旋转抵消了电极和二茂铁单元之间的距离。最后，我们还表明，没有法拉第电流观察到这些树突的两亲性组件，而同样的树突表现出显着的法拉第电流在非组装溶剂环境。
Whereas encapsulation of functional groups at the core of dendrimers is well-understood, very little is known about their intermediate layers or even the periphery. Here we report oil a systematic investigation of every layer of dendrimers by incorporating a single ferrocene unit in well-defined locations in dendrons. Site-specific incorporation of the ferrocene unit was achieved by utilizing the dendrimer sequencing methodology. We show here that the redox potential values of ferrocene at intermediate layers were remarkably different from those at the core and the periphery. Although redox potential values were location-dependent, no significant change in the rate of heterogeneous electron transfer (k(0)) was observed with respect to locations. This was attributed to the possibility that free rotation of dendrimer nullifies the distance between the electrode and ferrocene unit. Finally, we also show that no Faradaic current was observed for the amphiphilic assemblies of these dendrons, whereas the same dendron did exhibit significant Faradaic current in nonassembling solvent environments.