Chiral dendrimer encapsulated Pd and Rh

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Chiral dendrimer encapsulated Pd and Rh nanoparticles
Michael Pittelkow,a Theis Brock-Nannestad,a Kasper Moth-Poulsenb and
Jørn B. Christensen*a
Received (in Cambridge, UK) 22nd January 2008, Accepted 18th February 2008
First published as an Advance Article on the web 17th March 2008
DOI: 10.1039/b801215f
The synthesis of a series of chiral PAMAM dendrimers and the
formation of chiral dendrimer encapsulated metal nanoparticles
are described.
Expression of chirality is a common feature in materials of
both synthetic and natural origin. Homochirality of molecular
building blocks such as D-sugars and L-amino acids in macromolecular structures like DNA and proteins accounts for
many of the fascinating functions of biological systems. Chirality in artificial and naturally occurring macromolecular
systems has been studied extensively raising the question of
the origin of chirality in biological macromolecules.1,2
Chirality in metal nanoparticles is a sparsely explored
phenomenon mainly due to the lack of reliable preparative
procedures. DNA templated synthesis of Ag nanoparticles has
been accomplished using both single stranded DNA and
double stranded DNA.3 In an elegant study, Schaaff and
Whetten have isolated a series of gold–glutathione cluster
compounds using gel electrophoresis on polyacrylamide.4
The gold clusters were characterised by mass spectrometry
and CD and showed a large dependence in the chirality on the
molecular weights of the clusters. Au0 and Pd0 nanoparticles
stabilised by (S)-BINAP and (R)-BINAP have also been
prepared and the chirality of the Pd0 particles has been utilised
in the enantioselective hydrosilylation of olefins.5 Similarly
CdS quantum dots have been prepared using a D-penicillamine
stabiliser and the resulting particles also proved chiral.6 Chiral
mesoporous silica and chiral metal clusters prepared in the
presence of a virus-based structure have also been described
recently.7 The chiral nature of the stabilised metal particles in
the above mentioned studies could in principle be a result of
several different factors.5 Either the metal particle itself has
crystallised in a low symmetry (chiral) space group, or alternatively the chiral organic stabiliser has transferred its chirality to the metal particle either by imprinting of the metal
surface directly or through-space influences on the electronic
structure of the metal particle.
Since Meijer and co-workers described the dendritic box in
1994, many studies using molecular encapsulation in dendrimers have been disclosed, inspiring the use of dendrimers as
scaffolds for uses ranging from light-harvesting structures to
drug-delivery systems.8–10 Encapsulation of molecular species
inside dendrimers provides a fascinating route to well-defined
objects of nanometre dimensions depending on the size of the
dendrimer.11 These metal particles have potential uses in
optical devices, catalysis and drug-delivery to name a few.
Dendrimer encapsulated metal particles of well-defined sizes
have been reported for a number of different metals including
Pd, Pt, Au, Ag, Ni and Cu.12–14 The preparation of dendrimer
encapsulated metal nanoparticles follows the general protocol
for preparation explored in depth by Crooks and co-workers.
In brief, a metal salt is absorbed by the dendrimer and the
dendrimer encapsulated metal particle is formed by in situ
reduction of the metal salt by an external reducing agent
(Fig. 1).11 Dendrimer encapsulated metal particles in catalysis
have been a popular research target and recyclable systems
have been prepared for a number of reactions such as
hydrogenation of olefins,15 the Suzuki reaction,16 the Stille
reaction17 and the Heck reaction.18
Here we describe the use of a chiral poly(amido amine)
(PAMAM) dendrimer as a molecular scaffold for the encapsulation of Pd and Rh metal particles. The resulting chiral
particles have a mean diameter of 1.7 nm. We describe for the
first time a PAMAM dendrimer that has chirality both at the
core of the dendrimer and throughout the internal structure.
The surface of the chiral dendrimers is achiral and hydrophobic in nature. These features allow for the formation of
Department of Chemistry, University of Copenhagen,
Universitetsparken 5, Copenhagen Ø, Denmark. E-mail:
[email protected]; Fax: +45 35320112; Tel: +45 35320194
Nano-Science Center, Department of Chemistry, University of
Copenhagen, Universitetsparken 5, Copenhagen Ø, Denmark
2358 | Chem. Commun., 2008, 2358–2360
Fig. 1 Synthetic scheme for encapsulation of metal particles inside
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The Royal Society of Chemistry 2008
Fig. 3 Structure of the series of chiral PAMAM dendrimers (1–4).
Fig. 2
Retrosynthesis of chiral PAMAM dendrons and dendrimers.
dendrimer–metal complexes inside the dendrimers while at the
same time enhancing the solubility of these complexes in
organic solvents. As a consequence of these features, reduction
of the complexed metal atoms inside the chiral dendrimers
results in monodisperse dendrimer encapsulated metal nanoparticles.
The chiral PAMAM dendrimers were synthesised using a
protocol developed for the convergent synthesis of racemic
(internally branched) PAMAM dendrimers (Fig. 2).19 In brief,
selective BOC protection of ( )-1,2-diaminopropane followed
by a double conjugated addition of the free amino group in
neat benzyl acrylate gave the protected 2-wedge (BOC-2WBn). Synthetically, the BOC amino protection group and the
benzyl ester protection groups are orthogonal and separate
removal of the protection groups and coupling of these with
an amide coupling reagent (PyBOP) gave the 4-wedge (BOC4W-Bn). Boc deprotection of BOC-4W-Bn and coupling to the
benzyl-deprotected 2-wedge gave the 8-wedge (BOC-8W-Bn).
The core of the dendrimer (4) was synthesised by conjugate
addition of ( )-1,2-diaminopropane in neat benzyl acrylate.
The benzyl ester groups were removed by catalytic hydrogenation over Pd/C to give the tetracarboxylic acid. The dendrimers were assembled by BOC deprotection of the three
dendrons and amide coupling (using PyBOP as the coupling
reagent) to the tetracarboxylic acid core to give the series of
chiral PAMAM dendrimers (1–3) (Fig. 3).
Pd and Rh encapsulated metal particles were prepared
according to the procedure outlined in Fig. 1 with the chiral
PAMAM-32 dendrimer as the template.w Mixing 20 equivalents of Pd(OAc)2 or RhCl33.5H2O dissolved in 1 : 3 methanol
: chloroform with the dendrimer (1) resulted in a pale yellow
Pd2+–dendrimer complex or a pale red Rh3+–dendrimer
complex, respectively. These were reduced by addition of
NaBH4 in 1 : 3 methanol : chloroform to give pale brown
solutions of dendrimer encapsulated Pd0 or Rh0 metal particles ([email protected] and [email protected]). The solution
of metal particles was extracted with water, dried and evaporated to dryness. The resulting solids were freely soluble in
This journal is
The Royal Society of Chemistry 2008
dichloromethane but insoluble in alcohol. The metal particles
were conveniently stored in the solid state and retained their
solubility and monodispersity as tested over a period of several
In Fig. 4, the UV-Vis spectra of the chiral dendrimer
PAMAM-32, the [email protected] nanoparticles and the
[email protected] nanoparticles in dichloromethane solutions
are shown. The UV-Vis spectra of the [email protected] and
the [email protected] metal nanoparticles exhibit broad
absorption bands in the high energy part of the visible region
(up to B500 nm) (Fig. 4).20,21 These bands are ascribed to the
electronic structure of the nanoparticles and are thus not proof
of specific interactions with the dendrimer. The appearance of
the spectrum of the chiral dendrimer PAMAM-32 is illustrative of the general appearance of all spectra of the dendrons
and dendrimers shown in Fig. 2 and 3.
In Fig. 5, the CD spectra of the chiral dendrimer PAMAM32, the [email protected] nanoparticles and the [email protected] nanoparticles in dichloromethane solutions are
shown.22 The CD spectra (Fig. 5) shows that the UV-Vis
bands arising from the electronic structure of the metal
particles exhibit different absorptions dependent upon the
circular polarisation of the light, that is a Cotton effect. This
clearly illustrates that while the interaction between the nanoparticles and the dendrimer cannot be determined directly
Fig. 4 UV-Vis spectra of the chiral PAMAM-32-Bn dendrimer (1) in
CH2Cl2, the chiral [email protected] nanoparticles and the [email protected] nanoparticles.
Chem. Commun., 2008, 2358–2360 | 2359
are achiral. This represents an entirely new concept within the
field of chiral nanoparticles. The chirality transferred from the
dendrimer to the metal particles and the low polydispersity of
the particles makes this procedure attractive for the construction of chiral catalysts and chiral materials in general.
Notes and references
Fig. 5 CD spectra of the chiral PAMAM-32-Bn dendrimer (1) in
CH2Cl2, the chiral [email protected] nanoparticles and the
[email protected] nanoparticles.
Fig. 6 TEM picture of [email protected] nanoparticles.
from the UV-Vis spectra it can be seen from the CD-spectra.
The absorptions are not only indicative of the interactions
between the dendrimer and the nanoparticles but also of the
chiral electronic structure of the dendrimer encapsulated metal
particles. As a control experiment the Pd metal particles were
prepared using a racemic PAMAM dendrimer as the template
and this material was indeed CD silent.
Transmission electron microscopy (TEM) was performed
on the dendrimer encapsulated metal particles drop cast from
a dilute dichloromethane solution on Cu grids and revealed
the highly monodisperse nature of the dendrimer encapsulated
nanoparticles. The [email protected] particles have a mean
diameter of 1.7 nm as measured from 100 metal particles
(Fig. 6). This is in good agreement with the size expected
based on data reported for dendrimer templated metal particles in PAMAM dendrimers, and indicates that the metal is
indeed encapsulated inside the dendrimer and not merely
stabilized by the organic material.11
In conclusion, we have shown, in an unprecedented clean
and simple way, that dendrimer encapsulated metal particles
can be formed inside chiral PAMAM dendrimers. The chirality of the dendritic scaffold is transferred to the electronic
transition of the metal particles and a Cotton effect from the
metal nanoparticle UV-Vis bands appears. The coordination
of the nanoparticles to the inside of the dendrimer, and not, as
in the examples above, by the binding of chiral building blocks
to the exterior of a particle, is indicated by the observed CDsignal in a system where the surface groups on the dendrimer
2360 | Chem. Commun., 2008, 2358–2360
w Dendrimer encapsulated metal particles, general procedure: dendrimer 1 (10 mg, 0.00113 mmol) was dissolved in CHCl3 (0.2 mL) and
MeOH (0.1 mL) and the appropriate metal salt (0.0226 mmol, 20 eq.)
was added dissolved in CHCl3 (0.2 mL) and MeOH (0.1 mL). This
mixture was stirred for 30 minutes. Then NaBH4 (1.8 mg, 0.0452
mmol, 40 eq.) dissolved in CHCl3 (0.2 mL) and MeOH (0.1 mL) was
added and the mixture was stirred for 30 minutes. Water was added (3
mL) and the phases were separated. The organic phase was dried
(Na2SO4), filtered through paper and evaporated to dryness. TEM,
UV-Vis and CD were performed on solutions made in spectroscopy
grade CH2Cl2.
Instruments: TEM was recorded on a Philips CM-20 electron microscope operated at 200 kV. UV-Vis spectroscopy (Varian CARY 5E)
and CD spectroscopy (JEOL J-710 spectropolarimeter) were recorded
in the laboratories at the Department of Inorganic Chemistry,
University of Copenhagen.
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