Akademik Veri Yönetim Sistemi
Journal of Molecular Graphics and Modelling, cilt.146, 2026 (SCI-Expanded, Scopus)
Understanding how peripheral substituents control adsorption and electronic response is essential for the molecular design of porphyrin-based CO2-responsive materials. In this work, pristine porphyrin and eight substituted derivatives bearing CH3, CHO, CN, COOH, F, NH2, NO2, and OH groups were systematically examined toward CO2 adsorption. The optimized geometries show that CO2 adopts either surface-oriented configurations above the porphyrin core or edge-oriented arrangements near the substituents, depending on the local chemical environment. Among the studied systems, P-COOH and P-F exhibit the strongest adsorption energies (−0.15 eV), whereas P-CN shows the weakest interaction (−0.10 eV), indicating the most weakly bound and readily reversible adsorption. Although substituent identity substantially modifies the intrinsic frontier-orbital energies of the porphyrin frameworks, CO2 adsorption induces only minor HOMO-LUMO gap changes (−0.57 to 2.14%), consistent with limited electronic perturbation. Charge analysis reveals negligible charge transfer to CO2, while reduced density gradient analysis confirms that adsorption is dominated by weak noncovalent interactions. Importantly, the results reveal a clear substituent-dependent trade-off among binding strength, electronic signal modulation, and recovery behavior: P-COOH and P-F favor relatively stronger CO2 retention, P-CN is most suitable for rapid and reversible response, and P-CH3 and P-OH show the largest predicted sensing responses. These findings establish a practical structure-property framework for tuning CO2 adsorption and interfacial selectivity in functionalized porphyrins.