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Magnetic Circular Dichroism of Porphyrin Lanthanide M 3+ Complexes
Author(s) -
Andrushchenko Valery,
Padula Daniele,
Zhivotova Elena,
Yamamoto Shigeki,
Bouř Petr
Publication year - 2014
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22365
Subject(s) - lanthanide , chemistry , circular dichroism , magnetic circular dichroism , chirality (physics) , porphyrin , spectroscopy , absorption spectroscopy , density functional theory , metal , vibrational circular dichroism , crystallography , absorption (acoustics) , spectral line , photochemistry , computational chemistry , organic chemistry , materials science , physics , ion , chiral symmetry breaking , quantum mechanics , astronomy , nambu–jona lasinio model , composite material , quark
Lanthanide complexes exhibit interesting spectroscopic properties yielding many applications as imaging probes, natural chirality amplifiers, and therapeutic agents. However, many properties are not fully understood yet. Therefore, we applied magnetic circular dichroism (MCD) spectroscopy, which provides enhanced information about the underlying electronic structure to a series of lanthanide compounds. The metals in the M 3+ state included Y, La, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the spectra were collected for selected tetraphenylporphin (TPP) and octaethylporphin (OEP) complexes in chloroform. While the MCD and UV‐VIS absorption spectra were dominated by the porphyrin signal, metal binding significantly modulated them. MCD spectroscopy was found to be better suited to discriminate between various species than absorption spectroscopy alone. The main features and trends in the lanthanide series observed in MCD and absorption spectra of the complexes could be interpreted at the Density Functional Theory (DFT) level, with effective core potentials on metal nuclei. The sum over state (SOS) method was used for simulation of the MCD intensities. The combination of the spectroscopy and quantum‐chemical computations is important for understanding the interactions of the metals with the organic compounds. Chirality 26:655–662, 2014 . © 2014 Wiley Periodicals, Inc.