Ruthenium(II) Polypyridyl Complexes with 4,5-Diazafluorene
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versible reduction at –1.40 V is located on one of the two 2,2Ј-
bipyridine ligands on each metallic terminal, adding electrons
to the 2,2Ј-bipyridine localized LUMO+1 yielding the species
[{Ru(bpy·–)(bpy)}4(μ4-L4–)]. Similar to the oxidation process,
the reductions of the remote 2,2Ј-bipyridine appear at the same
potential, indicating no interaction between the four sites. The
third reduction appearing at –1.65 V is quasi-reversible and
yields the species [{Ru(bpy·–)2}4(μ4-L4–)]4–. Electro-
chemistry behaviors of complexes [{Ru(bpy)2}4(μ4-L2)]8+ and
[{Ru(bpy)2}4(μ4-L3)]8+ are similar to that of complex
[{Ru(bpy)2}4(μ4-L1)]8+.
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Three tetrapodal ligands derived from 4,5-diazafluorene-9-
one, and their corresponding tetranuclear RuII complexes were
synthesized and characterized. The UV/Vis absorption and
emission properties of the three complexes are dominated by
MLCT transitions and excited states. The three complexes ex-
hibit intense emission at around 575 nm originating from the
lowest energy MLCT excited state in EtOH/MeOH (4:1, v/v)
glassy matrix at 77 K. Electrochemical studies of the com-
plexes exhibit one single RuII-based oxidation wave. The spec-
troscopic and electrochemical properties of the three com-
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2+
plexes are somewhat different to those of Ru(bpy)3 due to
the different electronic nature of the tetrapodal ligands. These
properties of complexes [{Ru(bpy)2}4(μ4-L1)]8+ and
[{Ru(bpy)2}4(μ4-L2)]8+ are also somewhat different to those of
[{Ru(bpy)2}4(μ4-L3)]8+ due to the slightly variation of the
three bridging ligands. Electrochemical properties show little
interaction between the three RuII polypyridyl complexes. It is
well-documented that an interaction of a few reciprocal centi-
meters (which can not be noticed in spectroscopic and electro-
chemical experiments) is sufficient to cause fast intercompon-
ent electron or energy transfer processes,[39–43] so the three
complexes have potential applications in the area of photoin-
duced electron or energy transfer.
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We are grateful to the National Natural Science Foundation of China
(21261019) and the Yunnan Provincial Science and Technology
Department (2010ZC148) for financial support.
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