A heteroleptic push-pull substituted iron(II) bis(tridentate) complex with low-energy charge-transfer states.
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) T2 , (t2g )(4) (eg *)(2) ) and a low-spin ground state ((1) A1 , (t2g )(6) (eg *)(0) ). The intermediate triplet spin state ((3) T1 , (t2g )(5) (eg *)(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.
Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128 Mainz (Germany), Fax: (+49) 6131-39-27-277.
Andreas K C
AK
Mengel
Christoph
C
Förster
Aaron
A
Breivogel
Katharina
K
Mack
Julian R
JR
Ochsmann
Frédéric
F
Laquai
Vadim
V
Ksenofontov
Katja
K
Heinze
charge transfer; excited states; iron; ligand field splitting; tridentate ligands