title: Synthesis and characterization of a modified "picket fence" porphyrin complex - stronger π bonding interactions between Fe(ii) and axial ligands.
abstract: A new, modified "picket fence" porphyrin is synthesized and its bis(imidazole)-ligated iron(ii) derivative [Fe(MbenTpivPP)(1-MeIm)(2)] is investigated. X-ray structure determinations demonstrate that [Fe(MbenTpivPP)(1-MeIm)(2)] has structural features of a near planar porphyrin plane, a relative perpendicular ligand orientation, and one unusually large absolute ligand orientation (φ). The combination of these features leads to a new type of species that is different from previously reported analogues. Further structural examination reveals a strong correlation between the mutual ligand orientations (θ) and the axial Fe-N(Im) bond distances, which is detailed for the first time. Mössbauer spectroscopic characterization shows that the low spin derivative has a quadrupole splitting of 0.99 mm s(-1) at 100 K.
authors.affiliation: College of Materials Science and Opto-electronic Technology, University of Chinese Academy of Sciences, YanQi Lake, HuaiRou District, Beijing, 101408, China. jfli@ucas.ac.cn.
authors.forename: Baiyin
authors.initials: B
authors.lastname: He
authors.forename: Charles E
authors.initials: CE
authors.lastname: Schulz
authors.forename: Jianfeng
authors.initials: J
authors.lastname: Li