Ab-Initio Study of Circular Dichroism and Circularly Polarized Luminescence of Spin-allowed and Spin-forbidden Transitions: From Organic Ketones to Lanthanide Complexes

Abstract

<div><div><div><p>Complete and restricted active space self-consistent field (CAS-/RAS-SCF) wavefunction methods are applied for the calculation of circular dichroism (CD) and circularly polarized luminescence (CPL) of a series of molecules comprising four organic ketones, the chiral Cobalt(III) complex Λ-[Co(en)3]3+ and the Europium(III) complex [Eu(DPA)3]3–. The ab-initio results are in good agreement with the experimental data and previous results obtained with Kohn-Sham density functional theory in the case of the spin-allowed transitions. CD and CPL properties are calculated ab-initio for the first time for the spin-forbidden transitions of both a transition metal and a lanthanide complex.</p></div></div></div>

Luminescence, chiroptical, magnetic andab initiocrystal-field characterizations of an enantiopure helicoidal Yb(iii) complex

“…32 Such a procedure was successfully applied recently to obtained the CPL spectrum of an analogous Eu(III) tris -dipicolinate complex. 33 At 0 K, the calculated CPL spectrum exhibits a strong positive and a strong negative band corresponding to the 0' → 0 and 0' → 1 transitions, respectively.…”

Structure Determination of Europium Complexes in Solution Using Crystal-Field Splitting of the Narrow f–f Emission Lines

“… 46 These modifications enabled us to complete a series of TD-DFT calculations within the limitations of the laboratory-based calculational resources, while preserving the chiral configuration of the three β-diketonate ligands found in the crystal structure ( Figures 5 b and S6 ). 59 Figure 5 compares the theoretical CD spectrum of 2 in acetonitrile and its experimental CD spectra produced with isomers A – H , in which five Cotton bands with a −,+,–,+,– sequence were observed. When we compared the experimental CD spectrum of 2 with the theoretical CD spectrum produced for the most stable isomer G (panel a vs panel c of Figure 5 ), five Cotton bands with a −,+,–,+,– sequence in the experimental CD spectrum ( Figure 5 a) were successfully reproduced in the theoretical one ( Figure 5 c).…”