Finally: The X-ray crystal structure of the illusive unsubstituted iron(III) phthalocyanine ?-oxo(1)dimer. DFT-predicted Mössbauer quadrupole splitting and antiferromagnetic coupling constants for X-ray geometry
Abstract
The molecular structure of the unsubstituted iron(III) phthalocyanine ?-oxo(1) dimer ((PcFe)2O) was determined by single crystal X-ray diffraction. In agreement with the earlier speculations, the dimer has a bent (Fe-O-Fe angle is 152.4°) structure. The interplay between the p-p interactions and steric hindrances caused by the isoindole units led to the observed staggering angle of ?24° between two phthalocyanine ligands. The high-spin iron(III) centers are located significantly above the phthalocyanine N4 planes (0.57-0.58Å). Several DFT exchange-correlation functionals were used to calculate the absolute value and sign of the Mössbauer quadrupole splitting and antiferromagnetic coupling constant for X-ray determined geometry of (PcFe)2O. It was demonstrated that the hybrid functionals provide the correct sign of the electric field gradient and the magnitude of the antiferromagnetic coupling constant compared to the pure functionals.
Department(s)
Chemistry and Biochemistry
Document Type
Article
DOI
10.1142/S1088424624500263
Keywords
DFT calculations, iron, phthalocyanine, X-ray crystallography, ?-oxo dimer
Publication Date
5-1-2024
Recommended Citation
Gerasimchuk, Nikolay N.; Nemykin, Victor N.; and Muldowney, Breanna E., "Finally: The X-ray crystal structure of the illusive unsubstituted iron(III) phthalocyanine ?-oxo(1)dimer. DFT-predicted Mössbauer quadrupole splitting and antiferromagnetic coupling constants for X-ray geometry" (2024). Faculty Scholarship. 377.
https://bearworks.missouristate.edu/articles00/377
Journal Title
Journal of Porphyrins and Phthalocyanines
