Although the water-soluble fullerenes (and possibly their simple metabolites) are not acutely toxic, they are retained in the body for long periods, raising concerns about chronic toxic effects. The fact that fullerenes distribute rapidly to many tissues suggests that they may eventually be useful to deliver highly polar drugs through membranes to a target tissue, however, and they may even have applications in the delivery of drugs to the brain. Recent advances in fullerene synthetic chemistry may also make it possible to control fullerene absorption/excretion profiles in the future.
Mixed-valence states of μ-oxo-centered trinuclear iron
carboxylate complexes,
[Fe3O(CH2BrCO2)6(H2O)3]
(1),
[Fe3O(CH3CO2)6(H2O)3]·2H2O
(2), and
[Fe3O(CH2ClCO2)6(H2O)3]·3H2O
(3), were characterized by X-ray
crystallography and 57Fe-Mössbauer spectroscopy.
Compound 1 has a trapped-valence-type structure, i.e.,
one Fe(II)-type atom and two Fe(III)-type atoms. The central
Fe3O atoms construct nearly an isosceles triangle array
with
Fe−O bond distances of 1.86(1), 1.83(1), and 2.00(1)
Å at 293 K. In the case of compound 2, the X-ray
structure
shows good equivalence in geometry around the three iron atoms.
Results of X-ray crystallography of 1 and 2
are
consistent with the results of Mössbauer spectroscopy. The
Mössbauer spectra of 1 show a trapped-valence
state
below 296 K. The Mössbauer spectra of compound 2
are simulated using a three-site relaxation model where an
increased rate of intramolecular electron transfer is assumed among the
three iron atoms with an increase in temperature.
Black crystals of 3 were converted to red powders of
[Fe3O(CH2ClCO2)6(H2O)3]
(4) due to loss of all three crystal
water molecules when kept in air at ambient temperature.
Mössbauer spectra of the dehydrated compound 4
show
a temperature-independent trapped-valence state. On the other
hand, there are three quadrupole doublets in the
Mössbauer spectrum of the hydrated compound 3 measured
at 86 K, one of which was ascribed to an FeII state
and
the remaining two to an FeIII (FeIIIA and
FeIIIB) state. It is found that two of the three
doublets (FeII and FeIIIA)
converge without appreciable line broadening with an increase in
temperature, while the other doublet (FeIIIB)
remains
unchanged, indicating valence delocalization over the two iron atoms.
The X-ray structure of compound 3 also
indicates that valence delocalization takes place only between two iron
atoms. At 112 K the central Fe3O atoms
array with the Fe−O bond distances of 2.003(2) (Fe1),
1.853(2) (Fe2), and 1.849(2) Å (Fe3). A temperature
increase
to 293 K changes the bond distances to 1.957(3) (Fe1) and to
1.895(3) Å (Fe2), while the bond distance of Fe3−O
is almost unchanged (1.846(3) Å). There are intra- and
intermolecular hydrogen bonds formed by the crystal water
and coordinated water molecules in compound 3. The
results suggest that hydrogen-bonding interaction affects
the
local environment of iron atoms and induces valence delocalization
between the two iron atoms.
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