Description
In this talk, the use of computational chemistry to reveal the critical factors controlling the structure and properties of expanded porphyrins in different environments is presented. Through extensive density functional theory calculations, we demonstrated that the molecular topology is highly influenced by the number of π-electrons and the size of the macrocycle.[1] Aromaticity emerged as the key concept determining the electronic, magnetic and nonlinear optical properties of expanded porphyrins and accordingly, we proposed different methods to quantify the Hückel and the Möbius aromaticity. By using these descriptors, the structure-property relationships between the molecular topology, aromaticity and nonlinear optical properties was established and the optimum conditions for viable Möbius systems and promising molecular switches were determined.[4]Finally, I will show how quantum-chemical methods can be used for understanding and predicting the metalation effect in expanded porphyrins. By using energy decomposition analysis, we have recently found that the molecular topology of d8 metal complexes of hexaphyrins depends on the sensitive interplay between the intrinsic ligand strain and the metal-ligand interaction strain. These findings offer a new perspective to rationalize the experimental observations and we proposed several guidelines for designing novel complexes of hexaphyrins.[5]
| Period | 27 Sept 2016 |
|---|---|
| Event title | Workshop on Theoretical Chemistry 2016 |
| Event type | Conference |
| Location | Trujillo, PeruShow on map |
| Degree of Recognition | International |