Leret Sofía, Pouillon Yann, Casado Santiago, Navío Cristina, Rubio Ángel, Pérez Emilio M
IMDEA Nanociencia , Ciudad Universitaria de Cantoblanco , C/Faraday 9 , 28049 , Madrid , Spain . Email:
Departamento de Física de Materiales , Facultad de Químicas , UPV/EHU , San Sebastián , Spain.
Chem Sci. 2017 Mar 1;8(3):1927-1935. doi: 10.1039/c6sc03894h. Epub 2016 Nov 4.
Many applications of carbon nanotubes require their chemical functionalization. Both covalent and supramolecular approaches have been extensively investigated. A less trodden path is the combination of both covalent and noncovalent chemistries, where the formation of covalent bonds triggers a particularly stable noncovalent interaction with the nanotubes. We describe a series of naphthalene diimide (NDI) bisalkene molecules that, upon mixing with single-walled carbon nanotubes (SWNTs) and Grubbs' catalyst, undergo two different reaction pathways. On one hand, they ring-close around the SWNTs to form rotaxane-like mechanically interlocked derivatives of SWNTs (MINTs). Alternatively, they oligomerize and then wrap around the SWNTs. The balance of MINTs to oligomer-wrapped SWNTs depends on the affinity of the NDI molecules for the SWNTs and the kinetics of the metathesis reactions, which can be controlled by varying the solvent. Thorough characterization of the products (TGA, TEM, AFM, Raman, UV-vis-NIR, PLE, XPS and UPS) confirms their structure and shows that each type of functionalization affects the electronic properties of the SWNTs differently.
碳纳米管的许多应用都需要对其进行化学功能化。共价法和超分子法都已得到广泛研究。一条较少有人涉足的途径是将共价化学和非共价化学结合起来，其中共价键的形成会引发与纳米管的一种特别稳定的非共价相互作用。我们描述了一系列萘二亚胺（NDI）双烯烃分子，它们在与单壁碳纳米管（SWNTs）和格拉布催化剂混合时会经历两种不同的反应途径。一方面，它们在SWNTs周围发生闭环反应，形成类似轮烷的SWNTs机械互锁衍生物（MINTs）。另一方面，它们会发生低聚反应，然后缠绕在SWNTs周围。MINTs与低聚体包裹的SWNTs之间的平衡取决于NDI分子对SWNTs的亲和力以及复分解反应的动力学，这可以通过改变溶剂来控制。对产物的全面表征（TGA、TEM、AFM、拉曼光谱、紫外-可见-近红外光谱、PLE、XPS和UPS）证实了它们的结构，并表明每种功能化类型对SWNTs电子性质的影响各不相同。
