Effets électroniques des substituants périphériques sur la stabilité structurale des polyhedral oligomeric silsesquioxanes (POSS) : Une étude DFT
Mots-clés :
Polyhedral oligomeric silsesquioxane (POSS), DFT, stabilité thermodynamique, HOMO–LUMO gapRésumé
Les polyhedral oligomeric silsesquioxanes (POSS) constituent une classe majeure de nanostructures hybrides organiques-inorganiques. Malgré leur utilisation répandue, la maîtrise fondamentale de l'impact des effets électroniques des substituants sur la stabilité intrinsèque de la cage inorganique demeure insuffisamment éclaircie. Dans ce travail, une étude théorique systématique des dérivés octafonctionnalisés Si8R8O12 (R=Cl, CF3, OH, NH2, COOH et OCH3 ) est réalisée en théorie de la fonctionnelle de la densité (DFT) au niveau B3LYP/6-311+G(d). Les géométries optimisées, la structure électronique et les descripteurs de stabilité ont été analysés. Les résultats révèlent que les groupes fortement attracteurs (Cl, CF3 et COOH) induisent une contraction du squelette Si-O et renforcent la stabilité thermodynamique. L’analyse des écarts HOMO-LUMO, des énergies de stabilisation isodésmiques (ISE) et des indices NICS(0) confirme une haute stabilité électronique sans caractère aromatique. Une étude thermochimique composite G3B3 sur Si8H8O12, Si8Li8O12 et Si8F8O12 établit l’ordre de stabilité : Si₈F₈O₁₂ > Si₈H₈O₁₂ > Si₈Li₈O₁₂. Ces résultats fournissent des règles de conception rationnelle indispensables pour l'ingénierie de nouveaux nanomatériaux hybrides sur mesure.
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