Small-gas recognition by a β-Pyrrolic nitro-functionalized porphyrin: Energetics, orbital response, and noncovalent interactions
Chemical Physics, cilt.610, 2026 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 610
- Basım Tarihi: 2026
- Doi Numarası: 10.1016/j.chemphys.2026.113335
- Dergi Adı: Chemical Physics
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, INSPEC, Academic Search Ultimate (EBSCO), Engineering Source (EBSCO)
- Anahtar Kelimeler: DFT, Gas adsorption, Interfacial selectivity, Noncovalent interactions, β-Pyrrolic nitro-functionalized porphyrin
- Ankara Üniversitesi Adresli: Evet
Özet
Density functional theory was used to examine adsorption of C2H4, C2H6, CH4, CO, H2, and N2 on a porphyrin bearing four nitro groups directly attached at the β-pyrrolic positions. The optimized structures show gas-dependent binding modes: C2H4 and C2H6 prefer mixed surface/edge adsorption, CH4 binds mainly on the porphyrin surface, and CO, H2, and N2 adsorb near the β-pyrrolic nitro groups. Adsorption energies decrease in the order C2H6 (−0.17 eV) ' C2H4 (−0.16 eV) ' CH4 (−0.12 eV) ' CO (−0.06 eV) ' N2 (−0.04 eV) ' H2 (−0.02 eV), while positive Gibbs free energies indicate weak, reversible adsorption under ambient conditions. Frontier-orbital analysis reveals small HOMO-LUMO gap changes (−0.36 to +0.54%), but the LUMO is more gas-sensitive than the HOMO, with C2H4 and CO giving the strongest response. These results show that adsorption strength and electronic response are decoupled descriptors.