Abstract
Owing to the attractive potential applications of porphyrin assemblies in photocatalysis, sensors, and material science, studies presently concerning porphyrin aggregation are widely diffused. π–π stacking, H-bonding, metal coordination, hydrophobic effect, and electrostatic forces usually drive porphyrin interaction in solution. However, theoretical studies of such phenomena are still limited. Therefore, a computational examination of the different porphyrin aggregation approaches is proposed here, taking into account amphiphilic [5-{4-(3-trimethylammonium)propyloxyphenyl}-10,15,20-triphenylporphyrin] chloride, whose aggregation behavior has been previously experimentally investigated. Different functionals have been adopted to investigate the porphyrin dimeric species, considering long-range interactions. Geometry optimization has been performed, showing that for the compound under analysis, H-type and cation–π dimers are the most favored structures that likely co-exist in aqueous solution. Of note, frontier orbital delocalization showed an interesting interaction between the porphyrin units in the dimer at the supramolecular level.
Highlights
Porphyrin assemblies are widespread in nature, where they are engaged in essential processes, such as efficient transport or storage of oxygen through the blood plasma or electron transfer in photosynthesis
Over the course of our studies focused on the development of amphiphilic porphyrin-based surfactant-assisted, and deposition methods or pH-induced self-assembly protocol, among supramolecular systems, we largely used the “good–bad” solvent self-assembling method, by which others [15,16,17,18,19,20,21,22,23,24,25,26]
Over the course of our studies focused on the development of amphiphilic macrocycles are at first molecularly dissolved in a good solvent and a bad solvent is added to porphyrin-based supramolecular systems, we largely used the “good–bad” solvent self-assembling trigger the aggregation process.are
Summary
Porphyrin assemblies are widespread in nature, where they are engaged in essential processes, such as efficient transport or storage of oxygen through the blood plasma or electron transfer in photosynthesis. The choice of porphyrin-based building blocks to organize supramolecular systems is extremely advantageous for several reasons: (i) their chemical versatility supported by well-established synthetic methodologies; (ii) their distinctive optical features; and (iii) their invaluable photophysical and photochemical properties that enhance the assembled materials, with obvious impacts on the performance in technological applications. These chromophores can organize elaborated architectures by an assorted set of non-covalent interactions (i.e., π–π stacking, H-bonding, metal coordination, hydrophobic effect, and electrostatic forces) between the tetrapyrrolic macrocycles, mostly in J- or H-aggregated species, where aromatic platforms are stacked side by side and face to face, respectively. It is well known that red-shifted UV-vis absorptions with respect to those of monomeric form are associated with J-type aggregates, while their blue shifts are distinctive of H-aggregation
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
