Absorption and electrochemical properties are reported for the iron(II)
complex of the unusually substituted ligand
3,3″-bis(4-methylphenyl)-2,2′:6′,2″-terpyridine, along
with the structure determination of the complex by single-crystal X-ray
crystallography. Crystal data for
C67H64.5F12FeN7.5OP2,
M 1336.6: triclinic, a 12.768(3),
b 15.789(4), c 17.160(4) Å,
α 85.553(6), β 77.756(6), γ 66.754(5)˚,
V 3106.1(12) Å3, space group
P 1, Z 2, ρ 1.43 g
cm–3, µ 0.30 mm-1 for
λ 0.6849 Å, R 0.091 for 4456 observed
(I > 2σ(I) ) reflections,
wR2 0.241, Δρ1.68 e
Å–3. The structural analysis reveals that,
as observed in analogous bisterpyridineiron(II) complexes, the ligands adopt
the preferred meridional binding motif. As a result, the
‘pulling-in’ of the outer pyridine rings forces each pair of
3,3″ substituted tolyl groups to diverge, resulting in an average
distance between the tolyl methyl groups of c. 11.6
Å. The cyclic voltammetery of the complex in MeCN displays upon
oxidative scanning a reversible one-electron wave
(E˚ = + 0.99 V v.
s.c.e.) and three one-electron waves under reducing conditions
(E1˚ = –1.27 V,
E2˚ = –1.51 V,
E3˚ = –1.96 V
v. s.c.e.). The electronic spectrum in acetonitrile
contained an MLCT band centred at 571 nm, with a molar absorption coefficient
of 18210 M–1 cm–1.
When compared to similar phenyl-substituted terpyridine ligand iron(II)
complexes this is a relatively low value and is assigned to reduced electronic
delocalization throughout the terpyridine backbone.