Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor.
Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor.
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DOI：
10.1002/chem.201304882
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发表时间：
2014-05
期刊：
影响因子：
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通讯作者：
U. Wild;C. Neuhäuser;S. Wiesner;E. Kaifer;H. Wadepohl;Hans‐Jörg Himmel
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文献类型：
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作者：
U. Wild;C. Neuhäuser;S. Wiesner;E. Kaifer;H. Wadepohl;Hans‐Jörg Himmel
本文报道了氧化还原活性胍超碱的氢键聚集体的合成、结构和性质。可逆氢键通过氢供体单元的氧化而开启，并导致形成聚集体，其中氢键供体单元被两个氢键受体单元夹在中间。(受体单元的)进一步氧化再次导致解聚。聚集体的形成与明显的颜色变化有关，电子状态可以描述为氢转移过程中的冻结阶段。氢键受体碱度的进一步增加会导致去质子化反应。
Herein the synthesis, structures and properties of hydrogen-bonded aggregates involving redox-active guanidine superbases are reported. Reversible hydrogen bonding is switched on by oxidation of the hydrogen-donor unit, and leads to formation of aggregates in which the hydrogen-bond donor unit is sandwiched by two hydrogen-bond acceptor units. Further oxidation (of the acceptor units) leads again to deaggregation. Aggregate formation is associated with a distinct color change, and the electronic situation could be described as a frozen stage on the way to hydrogen transfer. A further increase in the basicity of the hydrogen-bond acceptor leads to deprotonation reactions.