la9b00204_si_001.pdf (2.11 MB)
Balancing Noncovalent Interactions in the Self-Assembly of Nonplanar Aromatic Carboxylic Acid MOF Linkers at the Solution/Solid Interface: HOPG vs Au(111)
journal contribution
posted on 2019-04-04, 12:33 authored by Kristen
N. Johnson, Matthew J. Hurlock, Qiang Zhang, K. W. Hipps, Ursula MazurThis
study explores directed noncovalent bonding in the self-assembly
of nonplanar aromatic carboxylic acids on gold and graphite surfaces.
It is the first step in developing a new design strategy to create
two-dimensional surface metal–organic frameworks (SURFMOFs).
The acid molecules used are tetraphenylethene-based and are typically
employed in the synthesis of three-dimensional (3D) MOF crystalline
solids. They include tetraphenylethene tetracarboxylic acid, tetraphenylethene
bisphenyl carboxylic acid, and tetraphenylethene tetrakis-phenyl carboxylic
acid. The two-dimensional structures formed from these molecules on
highly ordered pyrolytic graphite (HOPG) and Au(111) are studied by
scanning tunneling microscopy in a solution environment. The process
of monolayer formation and final surface linker structures are found
to be strongly dependent on the combination of the molecule and substrate
used and are discussed in terms of intermolecular and molecule–substrate
interactions, bonding geometry, and symmetry of the acid molecules.
In the case of linker self-assembly on HOPG, the molecule–substrate
interactions play a significant role in the resulting surface structure.
When the acid molecules are adsorbed on Au(111), the intermolecular
interactions tend to dominate over the weaker molecule–substrate
bonding. Additionally, the interplay of π–π interactions
and hydrogen bonding that directs the surface self-assembly on different
supports can be modified by varying the linker concentration. This
is particularly applicable for the case of the acid molecules adsorbing
on the Au(111) substrate. Precise control over predesigned surface
structures and orientation of the nonplanar aromatic carboxylic linkers
open up an exciting prospect for manipulating the direction of SURFMOF
growth in two dimensions and potentially in 3D.
History
Usage metrics
Categories
Keywords
surface linker structurespredesigned surface structuresNonplanar Aromatic CarboxylicinteractionHOPGMOFacid molecules adsorbingSURFMOFBalancing Noncovalent Interactionsscanning tunneling microscopyacid moleculestetraphenylethene tetrakis-phenyl carboxylic acidtetraphenylethene bisphenyl carboxylic acidtetraphenylethene tetracarboxylic acid
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC