作者:Maria del Carmen Gimenez-Lopez、Jules A. Gardener、Adam Q. Shaw、Agnieszka Iwasiewicz-Wabnig、Kyriakos Porfyrakis、Claire Balmer、Geraldine Dantelle、Maria Hadjipanayi、Alison Crossley、Neil R. Champness、Martin R. Castell、G. Andrew D. Briggs、Andrei N. Khlobystov
DOI:10.1039/b915170b
日期:——
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 Er3N@C80 and Sc3N@C80 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 C60. The endohedral fullerenes appear to be significantly less reactive towards the functionalisation than C60, however they bind in a similar manner to a gold surface as their dithiolane terminated C60 counterparts. The optical activity of Er3N@C80 molecules is preserved after attachment of the functional group. We report a splitting of the endohedral Er3+ emission lines due to the reduction in symmetry of the functionalised fullerene cage, as compared to the highly symmetrical icosahedral C80 cage of pristine Er3N@C80.
开发了一种通过 1,3-偶极环加成反应将二硫戊环基团连接到内嵌金属富勒烯上的方法。这种含硫官能团充当锚,能够在室温下直接从溶液相有效地将内嵌富勒烯固定在 Au(111) 表面上。官能化的富勒烯形成无序的单层,不表现出长程有序,这归因于二硫戊环锚定物与表面的牢固结合以及官能团的构象灵活性。内嵌富勒烯 Er3N@C80 和 Sc3N@C80 已被用作功能化和后续表面沉积的模型。它们对二硫戊环官能化的化学反应性及其表面行为已与 C60 进行了比较。与 C60 相比,内嵌富勒烯对官能化的反应性似乎明显较低,但它们以与二硫戊环封端的 C60 对应物类似的方式与金表面结合。 Er3N@C80 分子在连接官能团后保留了光学活性。我们报告了与原始 Er3N@C80 的高度对称的二十面体 C80 笼相比,由于功能化富勒烯笼的对称性降低而导致内嵌 Er3+ 发射线的分裂。