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Electron Flow in Large Metallomacromolecules and Electronic Switching of Nanoparticle Stabilization: Click Ferrocenyl Dentromers that Reduce AuIII to Au Nanoparticles
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-07-18 , DOI: 10.1002/chem.201802289
Qi Wang 1 , Fangyu Fu 1 , Angel M. Martinez-Villacorta 2 , Sergio Moya 2 , Lionel Salmon 3 , Amélie Vax 4 , Julien Hunel 1 , Jaime Ruiz 1 , Didier Astruc 1
Affiliation  

Click ferrocenyl‐terminal dentromers, a family of arene‐cored dendrimers with triple branching (9‐Fc, 27‐Fc, 81‐Fc, and 243‐Fc), reduce AuIII to ferricinium dentromer‐stabilized Au nanoparticles (AuNPs). Cyclic voltammetry studies in CH2Cl2 show reversible CV waves with some adsorption for the 243‐Fc dentromer and the number of redox groups found, 255±25, by using the Bard–Anson method, is close to the theoretical number of 243. The dentromers reduce aqueous HAuCl4 to water‐soluble ferricinium chloride dentromer‐stabilized AuNPs with core sizes between 30 and 47 nm. These triazolylferricinium dentromer‐stabilized AuNPs are reduced by cobaltocene to cobalticinium chloride and ferrocene dentromer weakly stabilized AuNPs together with a redshift of the AuNP plasmon. The weakness of the AuNP stabilization is characterized by dentromer extraction with CH2Cl2 along with irreversible AuNP agglomeration for the 9, 27, and 81‐ferrocenyl dentromer, with only the 243‐ferrocenyl dentromer‐AuNP withstanding this process. Altogether, this demonstrates the electronic switching of the dentromer‐mediated AuNP stabilization.

中文翻译:

大型金属大分子中的电子流和纳米颗粒稳定化的电子开关:单击将AuIII还原为Au纳米颗粒的二茂铁基树枝状大分子

单击二茂铁基末端树枝状大分子,这是具有三分支(9-Fc27-Fc81-Fc243-Fc)的芳烃核心树枝状大分子,可将Au III还原为铁den稳定的铁纳米级金纳米颗粒(AuNPs)。CH 2 Cl 2中的循环伏安法研究显示,可逆CV波对243-Fc树状大分子具有一定的吸附作用,使用Bard-Anson方法发现的氧化还原基团数目为255±25,接近理论值243。树枝状聚合物还原HAuCl 4水溶液可以制备水溶性的氯化铁,由大分子铁稳定的AuNP,其核心尺寸在30到47 nm之间。这些三唑基二茂铁稳定的金纳米粒子被钴茂还原为氯化钴和二茂铁的铁骨架弱稳定的金纳米粒子以及金纳米粒子的红移。AuNP稳定性的弱点是用CH 2 Cl 2提取树状大分子,以及9、27和81-二茂铁基大丁草的不可逆AuNP团聚,只有243-二茂铁基大丁草-AuNP可以经受该过程。总而言之,这证明了由大分子介导的AuNP稳定化的电子转换。
更新日期:2018-07-18
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