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

Abstract

A porphyrin derivative called 5,15-di­(4-carboxyphenyl)­porphyrin (H2DCPp) with carboxyl groups successfully self-assembled on a highly oriented pyrolytic graphite (HOPG) surface and its co-assembly structures with three kinds of pyridine molecules were investigated by scanning tunneling microscopy (STM) with atomic resolution. H2DCPp arranged in a long-range ordered structure, and both 1,4-bis (pyridin-4-ylethynyl) benzene (BisPy), 4,4′-bipyridine (BP) and 1,3,5-tris­(pyridin-4-ylethynyl) benzene (TPYB) molecules successfully regulated the host molecules as guest molecules. The well-organized model optimized by density functional theory (DFT) calculations reveals the detailed behavior of the assembly characteristics and regulation of porphyrin derivatives, which is helpful for the research and development of solar cells and nanodevices.

Co-assembly Behaviors of Flavonol Derivatives Induced by a Pyridine Derivative on HOPG via Hydrogen Bonding and Van der Waals Forces

“…In order to investigate the effect of pyridine derivatives on the self-assembly of 3-hydroxyflavone compounds, we introduced the linear BisPy molecules. A variety of molecular assemblies have been successfully regulated by BisPy molecules. − After obtaining the stable self-assembly structures of DHF and BDHF , we continued to deposit a droplet of BisPy solution in 1-phenyloctane, respectively. The assembly structure of DHF molecules did not change (Figure S3).…”

Symmetry of Pyridine Derivatives Controlled Two-Dimensional Nanostructural Diversity by Co-Assembly with Aromatic Carboxylic Acids

“…Self-assembly, as the kernel of supramolecular chemistry, provides a general and excellent approach to constructing functional nanomaterials at the molecular scale. , Admittedly, molecular self-assembly is a complex process which mainly involves molecule–molecule, molecule–substrate, molecule–solvent, and even solvent–substrate interactions. − Especially, noncovalent interactions play important roles in regulating various ordered assembled structures, including hydrogen bonds, π–π stacking, van der Waals forces, dipole–dipole, and metal–ligand interactions. − Among them, the hydrogen bonds serve as the common interactions to stabilize two-dimensional (2D) assembled architectures on surfaces because their directionality and diversity contribute to flexibly controlling the formation of molecular assembly. − For example, 1,3,5-trimesic acid (TMA) has been found to self-assembled into chicken-wire and flower structures according to the complementary hydrogen bonding sites. , With the invention of the scanning tunneling microscope (STM), studies on molecular self-assembly have made great strides and have been arising for several decades . In addition, in order to deepen the understanding of molecular assembly mechanisms, the coassembly behaviors of multiple component systems have gained more attention. , When particular molecules are involved in a self-assembled adlayer, a unique 2D nanostructure may be constructed owing to the cooperation and competition between various noncovalent interactions.…”

The self-assembly of a pair of low-symmetry tetracarboxylic acid molecules and their co-assembly with bridging molecules at the liquid–solid interface

“…In addition, the selectivity and directivity of hydrogen bonds are noteworthy aspects concerning molecular self-assembly, and the self-assembly structures driven by the hydrogen bonds are more predictable and controllable. [20][21][22][23][24][25][26] In particular, cyclic dimeric O-H⋯O hydrogen bonds between two carboxyl groups have been widely used in the construction of particular 2D supramolecular architectures at the liquid-solid interface. [27][28][29][30][31] For instance, with the dimeric hydrogen bonds between carboxyl groups as the main driving force of self-assembly, trimesic acid (TMA) molecules can form a typical honeycomb network structure; [32][33][34] tetracarboxylic acid molecules such as NN4A and H 4 ETTC can form a Kagomé or a quadrilateral network structure, respectively; 35,36 flexible carboxylic porphyrin derivative IPETPP containing eight carboxyl groups can form both Kagomé and quadrilateral network structures.…”