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observed at 86 ꢁC. The Tg of the iron-cluster copolymers
€
9 U.-P. Apfel, Y. Halpin, M. Gottschaldt, H. Gorls, J. G. Vos, W.
vary in a temperature range from 86.3 to 105.3 ꢁC (with a
Weigand, Eur. J. Inorg. Chem. 2008, 5112–5118.
heat capacity (DCp) of about 0.35 Jgꢂ1
K
ꢂ1) probably due to
10 M. Y. Darensbourg, W. Weigand, Eur. J. Inorg. Chem. 2011,
917–918.
a different content of [2Fe2S] clusters. On the one hand this
behavior can be explained by the decreased chain mobility
in cases of higher contents of the bulky cluster. On the other
hand differences may be deduced to a higher ‘‘crosslinking’’
of the bis(styrene) complex containing copolymers. Finally
one cannot exclude that the observed variations in the DSC
traces may also arise from differences in the molar mass of
the copolymers.
11 K. N. Green, J. L. Hess, C. M. Thomas, M. Y. Darensbourg,
Dalton Trans. 2009, 4344–4350.
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13 S. Ibrahim, P. M. Woi, Y. Alias, C. J. Pickett, Chem. Com-
mun. 2010, 46, 8189–8191.
14 X. Liu, X. Ru, Y. Li, K. Zhang, D. Chen, Int. J. Hydrogen
Energy 2011, 36, 9612–9619.
15 X. Ru, X. Zeng, Z. Li, J. D. Evans, C. Zhan, Y. Tang, L.
Wang, X. Liu, J. Polym. Sci. Part A: Polym. Chem. 2010, 48,
2410–2417.
CONCLUSIONS
Three different styrene-based monomers connected to a
model of the active site of the [FeFe]-hydrogenase were syn-
thesized. The modified styrene derivatives with a carbon
bridgehead atom could be successfully copolymerized by a
controlled radical polymerization technique. In contrast to
that, the nitrogen bridged complex could not be copolymer-
ized despite several attempts. All functional copolymers
show a moderate to even strong absorbance in the area of
the carbonyl-vibration in the IR-region, indicating the incor-
poration of the [2Fe2S]-hexacarbonyl-cluster. It could be
shown that the biomimetic metal centers keep their activity
and redox behavior after polymerization and inclusion into
the copolymer chain. Furthermore, electrocatalytic proton
reduction could be proven. The content of catalytic [2Fe2S]-
clusters could be determined using ASS-measurements and
1H NMR spectroscopy. With this work, we contribute to
efforts in immobilizing [FeFe]-hydrogenase mimics to readily
processable copolymers. We are convinced that our work
will support future developments in the field of polymer-
bound metallorganic catalysts, able to produce hydrogen in a
highly efficient manner.
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ACKNOWLEDGMENTS
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The authors like to thank U.P. Apfel for important discussions,
€
S. Kohn for AAS measurements, C. Friebe for CV investigations,
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R. Paulus for DSC analysis and G. Festag for SEC measurements.
Financial support of the Dutch Polymer Institute (DPI, technol-
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