⁵⁷Fe Mössbauer and DFT study of the electronic and spatial structures of the iron(ii) (pseudo)clathrochelates: the effect of ligand field strength

Abstract

Combined experimental 57Fe Mössbauer and theoretical DFT study of a series of iron(II)-centered (pseudo)macrobicyclic analogs and homologs was performed. The field strength of the corresponding (pseudo)encapsulating ligand was found to...

Isomorphous Structures of Iron(II) Clathrochelates Featuring Terminal σ-Hole Donor Sites and Exhibiting the Cl/Br/I/S Quadruple Heteroisostructural Exchange

“…All boron-capped iron­(II) tris-α-dioximates reported in this study are diamagnetic, as follows from consideration of their NMR spectra and analysis of the X-ray diffractometry (XRD) data. The observed diamagnetism of our clathrochelates agrees well with that identified for all known macrobicyclic iron­(II) tris-α-dioximates …”

“…The observed diamagnetism of our clathrochelates agrees well with that identified for all known macrobicyclic iron(II) tris-α-dioximates. 36 In the iron(II) tris-α-dioximates, the σ-holes on the halogen and sulfur atoms are directed in the same way (Figures 2 and S5), while the positively charged iron(II) site increases their depth.…”

Precise Fingerprint Determination of Vibrational Infrared Spectra in a Series of Co(II) Clathrochelates through Experimental and Theoretical Analyses

“…We have shown, for example, that for TDDFT, the use of the B3LYP/LANL2DZ geometries, but a combination of aug-cc-pVTZ for Co and cc-pVDZ for the rest of the molecule, permits an adequate prediction of electronic spectra . On the other hand, the use of XRD data (whose geometry has been shown here and previously to be accurately predicted via the B3LYP/LANL2DZ combination) with a large set of functionals (OLYP, RPBE, B3LYP, TPSS, BP86) and the Ahlrich’s TZV basis was excellent in predicting electron densities at Fe nuclei and therefore trends in the 57 Fe Mossbauer spectra …”

“…The Certainly, future work with the purpose of strengthening our computational methodology will be directed to the theoretical study not only of the cobalt-centered clathrochelates and pseudoclathrochelates 60 but also their iron-and rutheniumencapsulated analogs. Other complexes, such as the derivatives of the pseudomacrobicyclic boron-monocapped tris-pyrazoloximate and tris-pyridineoximate ligands and their encapsulating Likewise, different oxidation states, such as +1, +2 and +3, will be studied, thereby allowing to compute the redox potentials of these complexes and also reorganization energies.…”

“…67 On the other hand, the use of XRD data (whose geometry has been shown here and previously to be accurately predicted via the B3LYP/LANL2DZ combination 31 ) with a large set of functionals (OLYP, RPBE, B3LYP, TPSS, BP86) and the Ahlrich's TZV basis was excellent in predicting electron densities at Fe nuclei and therefore trends in the 57 Fe Mossbauer spectra. 60…”