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On the origin of circular dichroism in trigonal dihedral d 6 complexes of bidentate ligands containing only σ‐orbitals. A qualitative model based on a density functional theory study of Λ‐[Co(en) 3 ] 3+
Author(s) -
Fan Jing,
Ziegler Tom
Publication year - 2008
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.20527
Subject(s) - chemistry , density functional theory , dihedral angle , atomic orbital , crystallography , circular dichroism , denticity , time dependent density functional theory , molecular orbital , vibrational circular dichroism , ligand (biochemistry) , ligand field theory , computational chemistry , chirality (physics) , molecular physics , molecule , physics , quantum mechanics , symmetry breaking , crystal structure , hydrogen bond , electron , receptor , biochemistry , organic chemistry , ion , nambu–jona lasinio model , chiral symmetry breaking
Time‐dependent density functional theory (TD‐DFT) in conjunction with qualitative molecular orbital theory is employed to interpret the circular dichroism (CD) spectrum of Λ‐[Co(en) 3 ] 3+ . The simulated spectrum based on TD‐DFT is compared in details with the experimental data. Emphasis is put on a qualitative understanding of the origin of optical activity in σ‐bonded trigonal dihedral complexes with bidentate ligands in general. Rotatory strengths associated with the CD bands of both d‐d transitions and ligand‐to‐metal charge transfer (LMCT) are interpreted based on the metal–ligand σ‐interactions. These interactions are in turn analyzed in terms of symmetry unique overlaps between metal d‐ and symmetry ligand‐orbitals as well as the dependence of these overlaps on geometrical parameters of the complex. Chirality, 2008. © 2008 Wiley‐Liss, Inc.