Rate of interfacial electron transfer through the 1,2,3-triazole linkage
Rate of interfacial electron transfer through the 1,2,3-triazole linkage
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DOI：
10.1021/jp057416p
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发表时间：
2006-08-17
影响因子：
3.3
通讯作者：
Chidsey, Christopher E. D.
中科院分区：
文献类型：
--
作者：
Devaraj, Neal K.;Decreau, Richard A.;Chidsey, Christopher E. D.
测量了两个二茂铁和一个四苯基卟啉铁氧化还原物种通过末端的乙炔通过铜(I)催化的叠氮化物-炔环加成反应形成1，2，3-三氮唑键的电子转移速率。这种三氮唑形成反应的高产率、化学选择性、方便性和广泛的适用性使这种模块化组装策略非常有吸引力。通过改变电子转移桥的长度和共轭，以及改变单层中的稀释剂硫醇，得到了从大于60,000到1 S(-1)的电子转移速率常数。三氮唑和三氮唑酮基键为电子转移提供了与酯类似的电子耦合。通过使用模块耦合化学，可以在多个数量级上改变电子转移到许多不同氧化还原物种的速率，这为研究和控制电子向多电子氧化还原催化剂和需要控制电子传递的类似界面系统的传递提供了一种方便的方法。
The rate of electron transfer is measured to two ferrocene and one iron tetraphenylporphyrin redox species coupled through terminal acetylenes to azide-terminated thiol monolayers by the Cu(I)-catalyzed azide-alkyne cycloaddition (a Sharpless "click" reaction) to form the 1,2,3-triazole linkage. The high yield, chemoselectivity, convenience, and broad applicability of this triazole formation reaction make such a modular assembly strategy very attractive. Electron-transfer rate constants from greater than 60,000 to 1 s(-1) are obtained by varying the length and conjugation of the electron-transfer bridge and by varying the surrounding diluent thiols in the monolayer. Triazole and the triazole carbonyl linkages provide similar electronic coupling for electron transfer as esters. The ability to vary the rate of electron transfer to many different redox species over many orders of magnitude by using modular coupling chemistry provides a convenient way to study and control the delivery of electrons to multielectron redox catalysts and similar interfacial systems that require controlled delivery of electrons.