| Texto completo | |
| Autor(es): |
Piscelli, Bruno A.
;
Swithenbank-Michel, Tiger
;
Cormanich, Rodrigo A.
;
O'Hagan, David
;
Buhl, Michael
Número total de Autores: 5
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Physical Chemistry Chemical Physics; v. N/A, p. 12-pg., 2025-10-07. |
| Resumo | |
A series of GFN-xTB methods were benchmarked against high-level DFT and ab initio thermodynamic data for a set of conformational equilibria and driving forces for the formation of non-covalent complexes involving the Janus-face fluorocyclohexanes based on the all-syn-C6FnR12-n motif (n = 3, 5, 6). When used alone, GFN methods showed moderate performance, with mean absolute errors (MAEs) from the high-level benchmarks of approximately 2.5 kcal mol-1 for conformational equilibria and similar to 5.0 kcal mol-1 for molecular complexes. However, applying DFT-level single-point energy corrections on GFN-optimised geometries significantly improved the accuracy, reducing MAEs to similar to 0.2 and similar to 1.0 kcal mol-1 for the same systems. This hybrid approach achieves DFT-D3-level accuracy while maintaining a low computational cost, offering up to a 50-fold reduction in computational time. As such, it provides a new cost-efficient and accurate tool for the computational modeling of Janus-face systems. An illustrative application to a flexible system, C6F5H6O2C(CH2)3NHCOC6H2(OR)3, is reported (R = alkyl), highlighting the relative stabilities of folded and extended forms and their supramolecular assembly into helical stacks. (AU) | |
| Processo FAPESP: | 22/10156-7 - Estudo experimental e teórico dos efeitos estereoeletrônicos e arranjo supramolecular de compostos organofluorados |
| Beneficiário: | Bruno de Almeida Piscelli |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado Direto |
| Processo FAPESP: | 18/03910-1 - Estudos físico-químicos de compostos orgânicos fluorados: abordagens experimental e teórica |
| Beneficiário: | Rodrigo Antonio Cormanich |
| Modalidade de apoio: | Auxílio à Pesquisa - Jovens Pesquisadores |
| Processo FAPESP: | 23/14064-2 - Modelagem da interação de ciclohexanos Janus-face com dsDNA e ssDNA. |
| Beneficiário: | Bruno de Almeida Piscelli |
| Modalidade de apoio: | Bolsas no Exterior - Estágio de Pesquisa - Doutorado Direto |