Supramolecular and Chiral Effects at the Titanyl Phthalocyanine/Ag(100) Hybrid Interface
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- 作者：Stefano Colonna ; Giuseppe Mattioli ; Paola Alippi ; Aldo Amore Bonapasta ; Antonio Cricenti ; Francesco Filippone ; Paola Gori ; Anna Maria Paoletti ; Giovanna Pennesi ; Fabio Ronci ; Gloria Zanotti
- 刊名：Journal of Physical Chemistry C
- 出版年：2014
- 出版时间：March 13, 2014
- 年：2014
- 卷：118
- 期：10
- 页码：5255-5267
- 全文大小：1011K
- 年卷期：v.118,no.10(March 13, 2014)
- ISSN：1932-7455
文摘
Nonplanar titanyl phthalocyanine (TiOPc) molecules, characterized by a central, highly dipolar Ti鈥揙 group, can offer further degrees of freedom in tailoring the properties of hybrid organic鈥搃norganic structures. Here, we combine scanning tunneling microscopy and low-energy electron diffraction measurements with ab initio density functional theory calculations to investigate the interaction of TiOPc molecules with the Ag(100) surface. Isolated molecules are adsorbed with the macrocycle parallel to the surface in two different configurations: with the O atom pointing outward (UP configuration) or with the O atom pointing toward the surface (DOWN configuration). A different interaction of UP and DOWN molecules with the surface can account for their different orientation on the surface as well as for the observation of marked chiral effects only for UP molecules. Self-assembled domains of randomly mixed UP and DOWN molecules form at the monolayer coverage, driven by a subtle interplay between the molecule鈥搒urface interaction, the intermolecular dipolar attraction, and the side interaction between adjacent molecules. Chiral patterns of isolated molecules, observed by STM, are transferred to these domains. Remarkably, theoretical calculations disclose an interfacial nature of such chiral properties. Finally, a metallic behavior observed for the monolayer disappears for TiOPc molecules in a second layer, which are electronically decoupled from the substrate.