School of Chemistry, University of Nottingham, UKNG7 2RD.
Phys Chem Chem Phys. 2010 Jan 7;12(1):123-31. doi: 10.1039/b915170b. Epub 2009 Nov 11.
A method has been developed for the attachment of a dithiolane group to endohedral metallofullerenes via a 1,3-dipolar cycloaddition reaction. This sulfur-containing functional group serves as an anchor, enabling efficient immobilisation of endohedral fullerenes on Au(111) surfaces at room temperature, directly from the solution phase. The functionalised fullerenes form disordered monolayers that exhibit no long-range ordering, which is attributed to both the strong bonding of the dithiolane anchor to the surface and to the conformational flexibility of the functional group. Endohedral fullerenes Er(3)N@C(80) and Sc(3)N@C(80) have been used as models for functionalisation and subsequent surface deposition. Their chemical reactivity towards dithiolane functionalisation and their surface behaviour have been compared to that of C(60). The endohedral fullerenes appear to be significantly less reactive towards the functionalisation than C(60), however they bind in a similar manner to a gold surface as their dithiolane terminated C(60) counterparts. The optical activity of Er(3)N@C(80) molecules is preserved after attachment of the functional group. We report a splitting of the endohedral Er(3+) emission lines due to the reduction in symmetry of the functionalised fullerene cage, as compared to the highly symmetrical icosahedral C(80) cage of pristine Er(3)N@C(80).
已经开发出一种通过 1,3-偶极环加成反应将二硫杂环戊烷基团连接到笼状金属富勒烯内的方法。这个含硫官能团作为一个锚点，能够直接从溶液相中，在室温下将内笼金属富勒烯有效地固定在 Au(111)表面上。功能化的富勒烯形成无序单层，没有长程有序，这归因于二硫杂环戊烷锚与表面的强键合以及官能团的构象灵活性。已将 Er(3)N@C(80)和 Sc(3)N@C(80) 内笼富勒烯用作功能化和随后的表面沉积的模型。比较了它们对二硫杂环戊烷功能化的化学反应性及其表面行为与 C(60)的反应性和表面行为。与 C(60)相比，内笼富勒烯似乎对功能化的反应性明显降低，但它们与金表面的结合方式与二硫杂环戊烷端接的 C(60)类似。在连接官能团后，Er(3)N@C(80)分子的旋光活性得以保留。与原始的 Er(3)N@C(80)的高对称二十面体 C(80)笼相比，我们报告了由于功能化富勒烯笼对称性降低而导致内笼 Er(3+)发射线的分裂。
