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processes at electrode surface due to the excellent stability of the
ferrocenium cation. The metallacycle
contains 20 redox-active
units in the structure. The two reversible four-electron reductive
processes for the inner scaffold of perylene bisimide units were
hardly influenced by the supramolecular arrangement in the cyclic
voltametry. However, it was found that the redox properties of the
16 peripheral ferrocenyl subunits are strongly affected by sterical
constraints imposed by the square-type architecture, causing signal
splitting for the redox potential of ferrocenes. In total, 24 charges
were loaded onto this nanosize assembly. The interior cavity of
this nanosize assembly with redox active units organized in a
three-dimensional superstructure has the strong potential to act
as a redox-active functional material. The UV
54
vis spectra of these
squares in dichloromethane exhibit intense absorption bands
with maxima at 579, 543, and 452 nm, which are characteristic for
the perylene bisimide chromophore and the weak absorption of
ferrocene around 440 nm (
−
e
3
−
1
−
1
) is hidden by the
overlapping of the strong absorption band of perylene. However, the
fluorescence properties of the perylene bisimide chromophore are
strongly affected by the presence of ferrocenyl substituents.
= 91 dm
•mol
•cm
Ar
Ar
O
O
O
O
Ph
2
P
PPh
2
P
Ph
2
Pt
N
N
N
N
Pt
Ph
2
O
O
N
N
O
O
Ar
Ar
O
N
O
O
N
O
Ar =
Ar
Ar
53
Ar
Ar
O
O
O
O
O
O
O
O
O
Ar
Ar
Ar
Ar
O
Fe
54
O
N
O
O
N
O
Ar
Ar
O
O
N
N
O
O
Ph
2
P
Ph
2
P
Pt
N
N
N
N
Pt
PPh
2
Ph
2
P
O
O
O
O
Ar
Ar
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