Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
J Am Chem Soc. 2010 May 12;132(18):6392-401. doi: 10.1021/ja100065h.
The complementary use of spectroscopy and microscopy sheds light onto mutual interactions between semiconducting single wall carbon nanotubes (SWNT) and either a strong dendritic electron acceptor-perylenediimide-or a strong dendritic electron donor-phthalocyanine. Importantly, the stability of the perylenediimide/SWNT electron donor-acceptor hybrids decreases with increasing dendrimer generation. Two effects are thought to be responsible for this trend. With increasing dendrimer generation we enhance (i) the hydrophilicity and (ii) the bulkiness of the resulting perylenediimides. Both effects are synergetic and, in turn, lower the immobilization strength onto SWNT. Owing to the larger size of the phthalocyanines, phthalocyanine/SWNT electron donor-acceptor hybrids, on the other hand, did not reveal such a marked dependence on the dendrimer generation. Several spectroscopies confirmed that distinct ground- and excited-state interactions prevail and that kinetically and spectroscopically well-characterized radical ion pair states are formed within a few picoseconds.
光谱学和显微镜学的互补使用揭示了半导体单壁碳纳米管(SWNT)与强树枝状电子受体-苝二酰亚胺或强树枝状电子给体-酞菁之间的相互作用。重要的是,苝二酰亚胺/SWNT 电子给体-受体杂化物的稳定性随树枝状聚合物代数的增加而降低。这一趋势归因于两个因素。随着树枝状聚合物代数的增加,我们增强了(i)亲水性和(ii)所得苝二酰亚胺的体积。这两种效应是协同的,从而降低了它们在 SWNT 上的固定强度。另一方面,由于酞菁的尺寸较大,酞菁/SWNT 电子给体-受体杂化物并没有表现出对树枝状聚合物代数的这种显著依赖性。几种光谱学证实,存在明显的基态和激发态相互作用,并且在几皮秒内形成了动力学和光谱特征良好的自由基离子对态。