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A Heteroleptic Push–Pull Substituted Iron(II) Bis(tridentate) Complex with Low‐Energy Charge‐Transfer States
Author(s) -
Mengel Andreas K. C.,
Förster Christoph,
Breivogel Aaron,
Mack Katharina,
Ochsmann Julian R.,
Laquai Frédéric,
Ksenofontov Vadim,
Heinze Katja
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404955
Subject(s) - chemistry , ligand (biochemistry) , pyridine , density functional theory , photochemistry , ground state , electron paramagnetic resonance , spin states , photoexcitation , crystallography , computational chemistry , medicinal chemistry , atomic physics , excited state , inorganic chemistry , nuclear magnetic resonance , biochemistry , physics , receptor
A heteroleptic iron(II) complex [Fe(dcpp)(ddpd)] 2+ with a strongly electron‐withdrawing ligand (dcpp, 2,6‐bis(2‐carboxypyridyl)pyridine) and a strongly electron‐donating tridentate tripyridine ligand (ddpd, N , N ′‐dimethyl‐ N , N ′‐dipyridine‐2‐yl‐pyridine‐2,6‐diamine) is reported. Both ligands form six‐membered chelate rings with the iron center, inducing a strong ligand field. This results in a high‐energy, high‐spin state ( 5 T 2 , (t 2g ) 4 (e g *) 2 ) and a low‐spin ground state ( 1 A 1 , (t 2g ) 6 (e g *) 0 ). The intermediate triplet spin state ( 3 T 1 , (t 2g ) 5 (e g *) 1 ) is suggested to be between these states on the basis of the rapid dynamics after photoexcitation. The low‐energy π * orbitals of dcpp allow low‐energy MLCT absorption plus additional low‐energy LL′CT absorptions from ddpd to dcpp. The directional charge‐transfer character is probed by electrochemical and optical analyses, Mößbauer spectroscopy, and EPR spectroscopy of the adjacent redox states [Fe(dcpp)(ddpd)] 3+ and [Fe(dcpp)(ddpd)] + , augmented by density functional calculations. The combined effect of push–pull substitution and the strong ligand field paves the way for long‐lived charge‐transfer states in iron(II) complexes.

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