Issue 40, 2019

A dithiocarbamate anchoring group as a flexible platform for interface engineering

Abstract

The molecular organization and electronic properties of dithiocarbamate (DTC) anchored self-assembled monolayers (SAMs) linked to Au(111) substrates are studied by a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and state-of-the-art density functional theory calculations. For that, several piperidine/piperazine precursors with different architecture and substitution patterns are selected. The presented data show that the DTC anchor provides a useful building block for monomolecular self-assembly on coinage metals with both sulfur atoms bonded to the substrate in a way similar to what is usually observed for the more commonly applied thiolate docking group. The combination of the DTC group with the quite flexible piperidine/piperazine cyclic linkers results in a dense molecular packing with an upright orientation of the terminal moieties. The latter comprise phenyl rings bearing various substituents, which enables tuning the interfacial dipole over a wide range. Simulations on two prototypical DTC-docked SAMs help to better understand the experimental observations and provide insight into the local origin of the SAM-induced shifts in the electrostatic energy. In particular, a comparison of measured and simulated XP spectra reveals the significant contribution of the DTC group to the interfacial dipole.

Graphical abstract: A dithiocarbamate anchoring group as a flexible platform for interface engineering

Supplementary files

Article information

Article type
Paper
Submitted
11 Jun 2019
Accepted
24 Sep 2019
First published
04 Oct 2019
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2019,21, 22511-22525

A dithiocarbamate anchoring group as a flexible platform for interface engineering

E. Sauter, G. Nascimbeni, D. Trefz, S. Ludwigs, E. Zojer, F. von Wrochem and M. Zharnikov, Phys. Chem. Chem. Phys., 2019, 21, 22511 DOI: 10.1039/C9CP03306H

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