Communication
Macromolecular
Rapid Communications
wileyonlinelibrary.com 1 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.201400581
past.
[1]
By the application of external triggers, i.e., by
changing the solvent, temperature, or light, surface prop-
erties have been influenced in a fast and efficient way for a
manifold of novel functional materials comprising “smart
surfaces.”
[2,3]
Compared to these more common triggers,
reports about responsive polymeric structures address-
able by an electrical current or redox reagents are rather
scarce. Within that field, however, metallopolymers based
on ferrocene seem to be promising candidates due to
recent advances in their synthetic protocols, which led to
well-defined and also surface-anchored polymer architec-
tures.
[4–9]
Exemplarily, redox-responsive metallopolymers
have been used for the release of a dye from redox-respon-
sive nanocapsules,
[10–12]
for switching the surface wet-
tability and membrane gating by changing the polymer
oxidation state,
[13–15]
for addressing metallopolymer-based
A novel strategy for the preparation of poly(ferrocenylsilane) (PFS) immobilized on the surface of
cross-linked polystyrene (PS) nanoparticles is reported. The ferrocene-containing core/shell archi-
tectures are shown to be excellent candidates as preceramic polymers yielding spherical ceramic
materials consisting of iron silicide (Fe
3
Si) and metallic iron after thermal treatment. For this pur-
pose, dimethyl- and hydromethyl[1]silaferrocenophane monomers are polymerized by surface-
initiated ring-opening polymerization upon taking advantage of residual vinylic moieties at the
PS particle surface. A strategy for selective chain growth from the particle surface is developed
without the formation of free PFS homopolymer in solution. The grafted particles are characterized
using transmission electron microscopy (TEM) and dynamic light scattering (DLS). These particles
are excellent precursors for ceramics as studied by thermogravimetric analysis (TGA). The com-
position of the ceramics is studied using X-ray diffraction (XRD) measurements, while the mor-
phology is probed by scanning electron microscopy (SEM) revealing the original spherical shape
of the precursor particles. Obtained ceramic materials— predominantly based on iron silicides—
show ferromagnetic behavior as
investigated by superconducting
quantum interference device
(SQUID) magnetization measure-
ments at different temperatures.
Surface-Initiated Anionic Polymerization of
[1]Silaferrocenophanes for the Preparation
of Colloidal Preceramic Materials
Johannes Elbert, Haiko Didzoleit, Claudia Fasel, Emanuel Ionescu,
Ralf Riedel, Bernd Stühn, Markus Gallei*
J. Elbert, Dr. M. Gallei
Ernst-Berl Institut für Technische und Makromolekulare
Chemie, Technische Universität Darmstadt,
Alarich-Weiss-Straße 4, 64287, Darmstadt, Germany
E-mail: m.gallei@mc.tu-darmstadt.de
H. Didzoleit, Prof. B. Stühn
Institut für Experimentelle Physik Kondensierter Materie,
Technische Universität Darmstadt, Hochschulstraße 8, 64289,
Darmstadt, Germany
C. Fasel, Dr. E. Ionescu, Prof. R. Riedel
Materials Science Department, Technische Universität
Darmstadt, Alarich-Weiss-Straße 2, D-64287, Darmstadt,
Germany
1. Introduction
The design of surfaces featuring so-called stimuli-respon-
sive polymers has spurred intensive research in the recent
Early View Publication; these are NOT the final page numbers, use DOI for citation !!
Macromol. Rapid Commun. 2014, DOI: 10.1002/marc.201400581