Epitaxial Supramolecular Assembly of Fullerenes Formed by Using a Coronene Template on a Au(111) Surface in Solution Soichiro Yoshimoto Eishi Tsutsumi Ryuji Narita Yasujiro Murata Michihisa Murata Koichi Fujiwara Koichi Komatsu Osamu Ito Kingo Itaya 10.1021/ja0684848.s001 https://acs.figshare.com/articles/journal_contribution/Epitaxial_Supramolecular_Assembly_of_Fullerenes_Formed_by_Using_a_Coronene_Template_on_a_Au_111_Surface_in_Solution/3013606 Characteristic properties of the coronene layer formed on Au(111) for the epitaxial growth of various fullerenes are described. The electrochemical behavior of the coronene adlayer prepared by immersing a Au(111) substrate into a benzene solution containing coronene was investigated in 0.1 M HClO<sub>4</sub>. The as-prepared coronene adlayer on Au(111) revealed a well-defined (4 × 4) structure. Structural changes of the array of coronene molecules induced by potential manipulation were clearly observed by in situ scanning tunneling microscopy (STM). Supramolecularly assembled layers of fullerenes such as C<sub>60</sub>, C<sub>70</sub>, C<sub>60</sub>−C<sub>60</sub> dumbbell dimer (C<sub>120</sub>), C<sub>60</sub>−C<sub>70</sub> cross-dimer (C<sub>130</sub>), and C<sub>60</sub> triangle trimer (C<sub>180</sub>) were formed on the well-defined coronene adlayer on the Au(111) surface by immersing the coronene-adsorbed Au(111) substrate into benzene solutions containing those molecules. The adlayers thus prepared were characterized by comparison with those which were directly attached to the Au(111) surface. The C<sub>60</sub> molecules formed a honeycomb array with an internal structure in each C<sub>60</sub> cage on the coronene adlayer, whereas C<sub>70</sub> molecules were one-dimensionally arranged with the same orientations. The dimers, C<sub>120</sub> and C<sub>130</sub> molecules, formed an identical structure with <i>c</i>(11 × 4√3)<i>rect</i> symmetry. For the C<sub>130</sub> cross-dimer molecule, C<sub>60</sub> and C<sub>70</sub> cages were clearly recognized at the molecular level. It was difficult to identify the adlayer of the C<sub>180</sub> molecule directly attached to Au(111); however, individual C<sub>180</sub> molecules could be recognized on the coronene-modified Au(111) surface. Thus, the adlayer structures of those fullerenes were strongly influenced by the underlying coronene adlayer, suggesting that the insertion of a coronene adlayer plays an important role in the formation of supramolecular assemblies of fullerenes. 2007-04-11 00:00:00 C 180 molecules C 60 molecules C 70 cages scanning tunneling microscopy 0.1 M HClO 4. C 60 cage C 60 triangle trimer fullerene C 130 molecules Epitaxial Supramolecular Assembly coronene adlayer C 70 molecules STM C 180 molecule