Host guest chemistry and supramolecular doping in triphenylamine-based covalent frameworks on Au(111)

Steiner C, Fromm L, Gebhardt J, LIU Y, Heidenreich A, Hammer N, Görling A, Kivala M, Maier S (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Nanoscale Royal Society of Chemistry

Book Volume: 13

Pages Range: 9798-9807

Journal Issue: 21

DOI: 10.1039/d0nr09140e

Abstract

The post-synthetic modification of covalent organic frameworks (COFs) via host-guest chemistry is an important method to tailor their electronic properties for applications. Due to the limited structural control in the assembly of two-dimensional surface-supported COFs, supramolecular networks are traditionally used at present for host-guest experiments on surfaces, which lack structural and thermal stability, however. Here, we present a combined scanning tunneling microscopy and density functional theory study to understand the host-guest interaction in triphenylamine-based covalently-linked macrocycles and networks on Au(111). These triphenylamine-based structures feature carbonyl and hydrogen functionalized pores that create preferred adsorption sites for trimesic acid (TMA) and halogen atoms. The binding of the TMA through optimized hydrogen-bond interactions is corroborated by selective adsorption positions within the pores. Band structure calculations reveal that the strong intermolecular charge transfer through the TMA bonding reduces the band gap in the triphenylamine COFs, demonstrating the concept of supramolecular doping by host-guest interactions in surface-supported COFs. Halogen atoms selectively adsorb between two carbonyl groups at Au hollow sites. The mainly dispersive interaction of the halogens with the triphenylamine COF leads to a small downshift of the bands. Most of the halogens change their adsorption position selectively upon annealing near the desorption temperature. In conclusion, we demonstrate evidence for supramolecular doping via post-synthetic modification and to track chemical reactions in confined space. This journal is

Authors with CRIS profile

Christian Steiner Professur für Experimentalphysik (Rastersondenmikroskopie) Lukas Fromm Lehrstuhl für Theoretische Chemie Julian Gebhardt Lehrstuhl für Theoretische Chemie YI LIU Professur für Experimentalphysik (Rastersondenmikroskopie) Alexander Heidenreich Lehrstuhl für Organische Chemie I Natalie Hammer Lehrstuhl für Organische Chemie I Andreas Görling Lehrstuhl für Theoretische Chemie Sabine Maier Professur für Experimentalphysik (Rastersondenmikroskopie)

Involved external institutions

Ruprecht-Karls-Universität Heidelberg DE Germany (DE)

How to cite

APA:

Steiner, C., Fromm, L., Gebhardt, J., LIU, Y., Heidenreich, A., Hammer, N.,... Maier, S. (2021). Host guest chemistry and supramolecular doping in triphenylamine-based covalent frameworks on Au(111). Nanoscale, 13(21), 9798-9807. https://dx.doi.org/10.1039/d0nr09140e

MLA:

Steiner, Christian, et al. "Host guest chemistry and supramolecular doping in triphenylamine-based covalent frameworks on Au(111)." Nanoscale 13.21 (2021): 9798-9807.

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