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Synthesis and Characterization of Organometallic Coordination Polymer
Nanoshells of Prussian Blue Using Miniemulsion Periphery Polymerization

The preparation of organometallic coordination polymer nanoshells
is challenging, although the synthesis of metallopolymers in various
nanostructures has been explored intensively.1 Since Mann and his
co-workers synthesized nanoparticles (NPs) of cyanometallate
coordination polymers of Prussian blue (PB) using reverse micelles
for the first time,2 a number of materials including polymers,
biospecies, and silica have been used as media to confine the growth
of the particles for the synthesis.3 In contrast, efforts to vary PB
NPs from solid spheres to other nanoshapes are limited despite its
importance in the context of nanoscience and material applications.4
Talham and his co-workers have prepared two-dimensional PB
analogues at the air-water interface using Langmuir-Blodgett
techniques.5a Stiegman has produced nanocrystalline rods and disks
of PB analogues in a silica matrix.5b Porous alumina templates were
used to prepare one-dimensional PB nanostructures.5c,d But, to the
best of our knowledge, there is no report on the preparation of PB
nanoshells. Herein, we report a conceptually new method for the
synthesis of PB nanoshells with tunable size using miniemulsion
periphery polymerization (MEPP). As shown in Scheme 1, MEPP
involves the preparation of miniemulsion droplets using organometallic
surfactants, followed by a coordination polymerization at
the periphery of the droplets. We also discovered that the resulting
shell structure substantially improved the thermal stability of the
polymers.
         In a typical experiment, miniemulsion droplets with a pentacyanoferrate
periphery were prepared from a mixture of water, an
organometallic surfactant of poly(ethylene glycol)-b-poly(propylene
glycol)-b-poly(ethylene glycol) terminated with pentacyano(4-
(dimethylamino)pyridine)ferrate (EPE-Fe), toluene, and hexadecane
(water/EPE-Fe/toluene/HD ) 90.8:4:5:0.2 by weight). Upon the
addition of Fe3+, a dark blue color appeared indicating the formation
of PB coordination polymers. The suspension was colloidal stable
in water but could be precipitated in methanol. After centrifugation,
filtration, and drying, blue powders of PB nanoshells were obtained.
In a control experiment, when we added the miniemulsion to
methanol before coordination polymerization, no precipitation was
observed and the solution became clear, indicating the disassociation
of the surfactants.

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