title: Density functional theory studies on the structures and electronic communication of meso-ferrocenylporphyrins: long range orbital coupling via porphyrin core.
abstract: The molecular and electronic structures together with the electronic absorption spectra of a series of metal free meso-ferrocenylporphyrins, namely 5-ferrocenylporphyrin (1), 5,10-diferrocenylporphyrin (2), 5,15-diferrocenylporphyrin (3), 5,10,15-triferrocenylporphyrin (4), and 5,10,15,20-tetraferrocenylporphyrin (5) have been studied with the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. For the purpose of comparative studies, metal free porphyrin without any ferrocenyl group (0) and isolated ferrocene (6) were also calculated. The effects of the number and position of meso-attached ferrocenyl substituents on their molecular and electronic structures, atomic charges, molecular orbitals, and electronic absorption spectra of 1-5 were systematically investigated. The orbital coupling is investigated in detail, explaining well the long range coupling of ferrocenyl substituents connected via porphyrin core and the systematic change in the electronic absorption spectra of porphyrin compounds.
authors.affiliation: Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
authors.forename: Lijuan
authors.initials: L
authors.lastname: Zhang
authors.forename: Dongdong
authors.initials: D
authors.lastname: Qi
authors.forename: Yuexing
authors.initials: Y
authors.lastname: Zhang
authors.forename: Yongzhong
authors.initials: Y
authors.lastname: Bian
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang
mesh_terms: D004581:Electronics; D008670:Metals / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D011166:Porphyrins / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D008670:Metals; D011166:Porphyrins