Metalation and coordination reactions of 2H-meso-trans-di(p-cyanophenyl)porphyrin on Ag(111) with coadsorbed cobalt atoms

Abstract

We investigated the metalation and coordination reactions of Co with 2H-5,15-bis(para-cyanophenyl)-10,20-bisphenylporphyrin (2HtransDCNPP) on a Ag(111) surface by scanning tunneling microscopy. At room temperature (RT), 2HtransDCNPPs self-assemble into a supramolecular structure stabilized by intermolecular hydrogen bonding. The metalation of 2HtransDCNPP is achieved either by depositing Co atoms onto the supramolecular structure at RT, or, alternatively, by depositing the molecules onto a submonolayer Co-precovered Ag(111) surface with a subsequent heating to 500 K. In addition, the molecules coordinate to Co atoms through the N atoms in the peripheral cyano groups with a preference of isolated 4-fold coordination motifs at RT.

Addressing Environmental Challenges of Porphyrin Mixtures Obtained from Statistical Syntheses

“…With the successful application of our method for P1 mixtures, we wanted to explore the scope of our semi‐automated cascade; the impact on the environmental factor, as well as accompanying costs. For this purpose, we enlarged our library (Figure 6), by the synthesis of five more porphyrin mixtures ( P2 – P6 ), which comprise of commonly utilized unsymmetrical porphyrins [2,13–15,19,37–47] . The overall yields are summarized in Table 2, together with an overview on the purification parameters, obtained for all porphyrin mixtures.…”

“…For this purpose, we enlarged our library ( Figure 6), by the synthesis of five more porphyrin mixtures (P2-P6), which comprise of commonly utilized unsymmetrical porphyrins. [2,[13][14][15]19,[37][38][39][40][41][42][43][44][45][46][47] The overall yields are summarized in Table 2, together with an overview on the purification parameters, obtained for all porphyrin mixtures. Spectroscopic data of all isolated porphyrins are listed in the Supporting Information.…”

“…However, porphyrins deviating from A 4 skeleton-symmetry are often more interesting, because they offer peculiar optoelectronic properties. [12] Due to their structural features, they are interesting candidates in the construction of two-dimensional structures formed on active metal, or metal oxide surfaces, [13][14][15] or show potential as building blocks in three-dimensional framework architectures (MOFs and COFs). [16][17][18] Further, they can be utilized for the functionalization of nanomaterials, such as graphene, or other carbon nanoarchitectures.…”

Self-Assembled 2D-Coordination Kagome, Quadratic, and Close-Packed Hexagonal Lattices Formed from a Cyano-Functionalized Benzoporphyrin on Cu(111)

“…Porphyrins are omnipresent in nature. , They consist of a tetrapyrrolic macrocycle with a central cavity, which can coordinate two hydrogen atoms or a large variety of metal atoms. − Porphyrins have been shown to be versatile and stable building blocks for the construction of metal–organic coordination networks exhibiting different geometries, since their backbone can be tailored with specific functional end groups. Lately, the attachment of cyano-functionalized groups to porphyrins turned out to be particularly interesting because the partially negatively charged N atoms can interact through different bonding motifs with neighboring molecules. − In addition, benzoporphyrins have a variety of potential practical applications, such as organic near-infrared devices, − oxygen sensors, photodynamic therapy, organic thin-film transistors, − and dye-sensitized solar cells. , Despite this relevance, only very few investigations of their adsorption behavior on different metal surfaces have been reported to date. − …”

Conformation Controls Mobility: 2H‐Tetranaphthylporphyrins on Cu(111)

“…[12][13][14] Scanning tunneling microscopy (STM) has been proven as a powerful tool to investigate such arrangements, their intramolecular conformation and their electronic structure. [13,15] Extensive studies [2] have shown that the conformation and supramolecular arrangement strongly depend on the substrate, [16,17] molecular coverage, [18] presence and nature of a coordinated metal atom, [19,20] heat treatments [13,21] and functional side groups. [22] In this regard, 2H-tetraphenylporphyrin (2HTPP) has become a well-understood reference system.…”