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DS: Fachverband Dünne Schichten

DS 15: Organic Thin Films, Organic-Inorganic Interfaces I (joint session DS/CPP)

DS 15.1: Vortrag

Dienstag, 17. März 2020, 09:30–09:45, CHE 91

Shape controlled assembly of carboxylic acids: intercalation into molecular nanotunnels — Rodrigo Ortiz de la Morena¹, Andika Asyuda², Hao Lu², Hannah Aitchison¹, Kelly Turner¹, Stephen M. Francis¹, •Michael Zharnikov², and Manfred Buck¹ — ¹EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, United Kingdom — ²Angewandte Physikalische Chemie, Universität Heidelberg, 69120 Heidelberg, Germany

Binary self-assembled monolayers (SAMs) combining a Y-shaped aromatic carboxylic acid (CA), 1,3,5-benzenetribenzoic acid (H3BTB), and a cage-type alicyclic CA, adamantane CA (AdCA), were prepared by molecular adsorption from solution on Au substrates modified by underpotential deposition of Ag. These SAMs exhibit a pronounced dependence of their structure on the assembly protocol. Exposing an AdCA SAM to H3BTB results in the disordered arrangements. In contrast, exposing an H3BTB SAM to AdCA doesn't seemingly affect the highly regular row structure of the native H3BTB layer, with no signs (STM) of AdCA adsorption. However, spectroscopic analysis reveals its presence, suggesting that the AdCA molecules are hidden in the nanotunnels of the H3BTB monolayer. Additional evidence for this hypothesis is provided by appearance of densely packed and highly ordered AdCA monolayer upon local removal of H3BTB. Formation of such a compact layer is explained by expulsion of AdCA from the H3BTB nanotunnels of the surrounding intact mixed SAM, driven by release of stress in the nanotunnels built up when AdCA is intercalated.