Self-Assembly of a Flexible Porphyrin Derivative Containing Tetra Isophthalic Acids and Host–Guest Interaction at the Liquid/Solid Interface

Abstract

This paper investigates the self-assembly of a flexible porphyrin derivative called 1,3-isophthalic acid-5-ether-4-tetraphenyl porphyrin at the interface of 1-heptanoic acid/highly oriented pyrolytic graphite (HA/HOPG). We observed that the porphyrin derivative shows an obvious concentration effect by scanning tunneling microscopy (STM): a rhombic structure appears at higher concentration and a flower structure at lower concentration. Then, we deposited coronene (COR) on the selfassembly templates, and the result showed only one host−guest co-assembled structure. Utilizing density functional theory, we also revealed the formation mechanism of different assembled structures.

Regulation of a Porphyrin Derivative Containing Two Symmetric Benzoic Acids by Different Pyridines

“…20,21 Due to the selectivity and saturation of hydrogen bonding, an increasing number of research have reported that porphyrin with a carboxyl functional group interacts with other molecules by hydrogen bonding to form supramolecular nanostructures. 8,13,15,22 Scanning tunneling microscopy (STM) with atomic resolution is considered to be the most effective method to investigate the molecular dynamics of assembly at solid/liquid interfaces, 23−28 and the regulation behavior of guest molecules, which impact the host molecules can be observed in real-time by STM under an ambient environment. 29−34 Hou et al used STM to detect porphyrin derivatives with side chain groups not only to obtain a self-assembled structure of H 2 TCPp under the action of hydrogen bonds but also to successfully regulate the host molecule by introducing dipyridine as a guest molecule.…”

“…It is important for us to know that porphyrin and porphyrin derivatives are famous for their optical and electrical performances, − which play a key role in photocatalytic , and electroluminescent materials, molecular sensors, solar cells, , etc. Besides, porphyrin derivatives have been considered seriously for their thermal stability and rigidity in molecular functional design and device assembly .…”

“…These interactions are noncovalent forces, which include hydrogen bonding, π–π stacking effect, van der Waals interaction, metal–ligand coordination, and so on. − Supramolecules are able to self-regulate and thus balance the forces between molecules and molecules, and molecules and substrates to reach the equilibrium state ultimately . The investigation on porphyrin assemblies through hydrogen bonding on a two-dimensional surface has become a hot topic of study. , Due to the selectivity and saturation of hydrogen bonding, an increasing number of research have reported that porphyrin with a carboxyl functional group interacts with other molecules by hydrogen bonding to form supramolecular nanostructures. ,,, …”

Scanning Tunneling Microscopy and Computational Simulation Studies of a Fluorenone-Based Organic Optoelectronic Material

“…In recent years, surface supramolecular self-assembly has been an intensively studied topic owing to its potential applications including surface modification, molecular-based devices, and two-dimensional (2D) crystal engineering. − Self-assembly is an effortless means for surface patterning, which involves reversible noncovalent interactions, and is a process where molecules adsorb onto and desorb from an atomically flat surface, for example, highly oriented pyrolytic graphite (HOPG), Au (111), Ag (111), and Cu (110). − The underlying driving forces include hydrogen bonds, halogen bonds, van der Waals interactions, and π–π attractions. − Scanning tunneling microscopy (STM) is the main analytical tool used due to its submolecular resolution.…”

Minor adjustments in the chemical structures of pyridine derivatives induced different co-assemblies by O–H⋯N hydrogen bonds

“…Because of the stronger selectivity and directionality of hydrogen bond, the carboxylic acid-based nanostructures were formed at the interface and many external environmental factors, such as temperature, 9 concentration, 10 electric field, 11 and solvent, 12 were also imposed to regulate the original self-assembly. Except for the mentioned external environmental factors, introducing various adsorbates, such as carboxylic acid, 13 and pyridine derivatives 14 into the original acid-based self-assembly system could also construct varied co-assembly structures by breaking the original O–H⋯O hydrogen bond and forming new non-covalent interactions.…”