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J Nanopart Res (2010) 12:1307–1318

DOI 10.1007/s11051-010-9862-0

RESEARCH PAPER

Permanent magnetism in phosphine- and chlorine-capped


gold: from clusters to nanoparticles
Miguel A. Muñoz-Márquez • Estefanı́a Guerrero •
Asunción Fernández • Patricia Crespo • Antonio Hernando •

Raquel Lucena • José C. Conesa

Received: 20 September 2009 / Accepted: 20 January 2010 / Published online: 6 February 2010
Ó Springer Science+Business Media B.V. 2010

Abstract Magnetometry results have shown that Keywords Gold clusters  Gold nanoparticles 
gold NPs (*2 nm in size) protected with phosphine EPR spectroscopy  SQUID magnetometry 
and chlorine ligands exhibit permanent magnetism. Ferromagnetic behaviour
When the NPs size decreases down to the subnano-
metric size range, e.g. undecagold atom clusters, the
permanent magnetism disappears. The near edge
structure of the X-ray absorption spectroscopy data
points out that charge transfer between gold and the Introduction
capping system occurs in both cases. These results
strongly suggest that nearly metallic Au bonds are Currently, many nanoscale applications such as
also required for the induction of a magnetic electronic devices, systems with catalytic properties,
response. Electron paramagnetic resonance observa- magnetic and optical mechanisms, and biological
tions indicate that the contribution to magnetism from systems (e.g. Andres et al. 1996; Valden et al. 1998;
eventual iron impurities can be disregarded. Sun et al. 2000; Boyen et al. 2002; Daniel and Astruc
2004; Turner et al. 2008) include transition metal
nanoparticles (NPs) as essential parts to perform their
function. Despite the widespread study and applica-
tion of these particular systems, there are still many
M. A. Muñoz-Márquez (&)  E. Guerrero  A. Fernández unknowns to be addressed regarding the solid-state
Instituto de Ciencia de Materiales de Sevilla (CSIC-US), properties and structure of capped transition metal
Av. Americo Vespucio 49, 41092 Sevilla, Spain
NPs (Whetten and Price 2007), for instance, their
e-mail: miguel.angel@icmse.csic.es
magnetic properties which can certainly help the
P. Crespo  A. Hernando understanding of essential questions in magnetism. It
Instituto de Magnetismo Aplicado (UCM-ADIF-CSIC), is known that due to size and surface effects that
P.O. Box 155, 28230 Las Rozas, Madrid, Spain
appear when the system size is reduced down to the
P. Crespo  A. Hernando nanometre range, e.g. the electronic properties of NPs
Departamento de Fı́sica de Materiales, UCM, are significantly different from bulk-like systems of
Av. Complutense s/n, 28040 Madrid, Spain the very same materials (Alivisatos 1996); however,
sometimes not only the system size is the key factor in
R. Lucena  J. C. Conesa
Instituto de Catálisis y Petroleoquı́mica (CSIC), Marie the physical properties and even the capping systems
Curie 2, Campus de Cantoblanco, 28049 Madrid, Spain play an important role in this profound change of the

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electronic structure (Zhang and Sham 2002). There- a highly reproducible and straightforward synthesis
fore, further investigations of the parameter space, procedure, it is not free of experimental difficulties.
which define the physical and chemical properties of In fact, it has been proved almost impossible to obtain
nanoscale systems, are always welcomed. subnanometric gold clusters using this synthesis
Regarding the NPs’ magnetic properties, it is now method which would justify the importance of the
widely accepted that a ferromagnetic-like behaviour synthesis methods developed by Weare et al. (2000)
is observed in one-dimensional nanoscale systems for small phosphine-stabilized Au NPs (diameter *2
such as gold, silver, palladium and copper which are nm) and, the procedures established by Bartlett et al.
diamagnetic in their bulk-like form. This claim leans (1978) to obtain phosphine-capped undecagold clus-
on a wealth of experimental results already published ters (subnanometric particles with a diameter around
in world-leading scientific journals (e.g. Shinohara 0.8 nm) that have played a very important role in the
et al. 2003; Sampedro et al. 2003; Crespo et al. 2004; research presented in this article. These synthesis
Yamamoto et al. 2004; Negishi et al. 2006; Suber methods allowed the fabrication of smaller particles
et al. 2007; Dutta et al. 2007; Garitaonandia et al. than the ones obtained by the Brust method and, in
2008; de la Venta et al. 2009), performed by wholly addition, they have the potential of exchanging the
independent research groups throughout the world. In phosphine shell with a protecting thiolated ligand
addition, this experimental work is now supported by layer (Song et al. 2003; Woehrle and Hutchison
recent theoretical total energy calculations (Gonzalez 2005); so the final result is a set of very small thiol-
et al. 2006; Luo et al. 2007; Michael et al. 2007) capped gold NPs or clusters.
which yielded encouraging results on size-dependent Moreover, the obtained NPs have been subject of
magnetization and spin symmetry-breaking that controversy regarding their magnetic properties
would explain the experimental results found for which some authors have ascribed to natural occur-
thiol-capped gold and silver nanoparticles. Probably, ring iron impurities that can be found in the reagent
the most striking advance at the light of the latest grade chemicals used across the synthesis process or,
magnetization studies based on element-specific as a result of using stainless steel tools whilst
techniques (Yamamoto et al. 2004; Negishi et al. manipulating the synthesis products and reactants
2006; Garitaonandia et al. 2008; de la Venta et al. (Abraham et al. 2005). However, it has been demon-
2009), such as X-ray magnetic circular dichroism strated that superparamagnetic iron impurities cannot
(XMCD) and Mössbauer spectroscopy, is that it has be responsible of the ferromagnetic behaviour in gold
been unequivocally determined that the gold atoms NPs (Crespo et al. 2006). The electron paramagnetic
neighbouring the chemisorption site at the nanopar- resonance (EPR) studies carried out in this investi-
ticle surface are the carriers of the magnetic moment. gation are key to probe the magnetic state of eventual
At this point, it has to be mentioned that all the impurities and, most important, to check their role on
previous studies mainly concern thiol-capped transi- the macroscopic magnetic behaviour.
tion metal nanoparticles and, as a result, the magnetic The structural and electronic properties of phos-
behaviour has been partly attributed to the charge phine-capped clusters and nanoparticles have been
transfer effect measured in the metal-S bond (Guer- deeply studied in the past (Weare et al. 2000; Bartlett
rero et al. 2007); including the fact that magnetism et al. 1978; Mingos 1976; Briant et al. 1981; Teo
was not observed in polymer-like gold compounds et al. 1992; Mingos 1996; Schmid 2008). However,
such as Au2S. Of course, as it will be discussed later, nobody before has explored the magnetic properties
this is not the only effect responsible of the of these systems in order to tackle the eventual
ferromagnetic-like behaviour. However, the well- relationship between the magnetic behaviour and the
known Brust method used to synthesize highly electronic/atomic structure. Moreover, there is a
monodisperse thiol-capped gold NPs from gold salt long-standing issue regarding the physical and chem-
(HAuCl4) reduction (Brust et al. 1994) has lead to a ical properties of these nanomaterials where the
widespread use and thorough study of the Au–S bond driving factors of the thermodynamic stability are
properties in nanometre-size systems, being these still unknown (Walter et al. 2008). These were the
gold-thiolate species the building blocks of many reasons that lead us to study the magnetic properties
self-assembled systems. Despite the Brust method is of phosphine-capped gold nanoparticles and clusters.

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As previously said, the nanoparticle surface atom nAu-TPP synthesis


bonding with the capping ligand is not the unique
concurring factor in the emergence of a ferromag- Phosphine-chlorine-capped Au NPs could be directly
netic-like behaviour in gold NPs. The size effect is obtained from HAuCl4 reduction in presence of
also a key point: the nanoparticle diameter is very triphenylphosphine (PPh3 or TPP), using NaBH4 as
similar to the wavelength of the confined electrons in reducing agent. The synthesis method used was first
the nanoparticle and this will determine many of the reported by Weare et al. (2000) which is a modifica-
physical properties of these particular systems at the tion of the well-known Brust method (1994). Au(III) is
quantum level. In addition, the ferromagnetic-like transferred from an aqueous solution of 0.2 g of
behaviour shall be strongly linked to the surface HAuCl4 in 12 mL of milli-Q water to degassed and
effects originated by the dramatic increase of atoms dried toluene; a solution of 0.28 g of tetraoctylammo-
that lose the bulk 3D symmetry in the NP surface; the nium bromide in 12 mL of toluene was used as the
atoms in the surface are only constrained in a 2D phase-transfer agent. The mixture is strongly stirred
fashion, hence, the NP physical properties undergo for 5 min whilst 0.46 g of PPh3 are added to the
significant changes associated to a modification in the solution which is further stirred for 10 more minutes. A
chemical environment and atomic structure. For fresh solution of NaBH4 (0.4 g of solute in 2 mL of
instance, considering the thiol-capped NPs, due to a milli-Q water) is quickly added whilst stirring then, the
huge increase in the mobility of the thiol-Au species mixture is continuously stirred for three hours. The
(Yu et al. 2006), the bonding of the sulphur atom in organic phase is then separated from the aqueous
the thiol head to a gold surface atom leads to a deep phase. Toluene is removed under reduced pressure by
change of the outermost surface atoms structure means of a rotary evaporator. The solid was precip-
which necessarily must involve a dramatic modifica- itated with hexane and, finally, filtered and washed
tion of the electronic structure. with hexane and MeOH/H2O.

Sample characterization
Experimental details
Particle characterization using elemental analysis,
Sample preparation ICP, TEM and SEM

Au11-TPP synthesis Aliquots of the synthesized nanoparticles were


dropped onto the carbon film on a 200-mesh copper
This subnanometric gold cluster is synthesized by grid and air dried. Nanoparticles were imaged
reduction of the AuCl(PPh3) precursor which was employing a Philips CM200 TEM microscope work-
synthesized according to the procedure described by ing at 200 kV at the Microscopy Service of the
Braunstein et al. (1990). Following the synthesis Instituto de Ciencia de Materiales de Sevilla. The
method established by Bartlett et al. (1978), 0.18 g approximate particle size distribution histograms were
of Au(PPh3)Cl are dissolved in 8 ml of absolute measured using image analyser software that deter-
ethanol and then reduced with a solution of NaBH4 in mines the cluster radii from a digital image of the
ethanol (0.0137 g of solute in 2 mL of solvent) over micrographs. The chemical composition by elemental
a 15 min period whilst the reducing agent is slowly analysis in a LECO CNS-2000 and ICP-MS in a
added under nitrogen atmosphere. The mixture is Thermo Elemental X-7 was determined at the Centro
then stirred for 2-h. The formed solid is precipitated de Investigación, Tecnologı́a e Innovación de la
with hexane and, filtered and washed with CH2Cl2/ Universidad de Sevilla (CITIUS). In addition, the
hexane. The remaining solid is dissolved in CH2Cl2 chemical composition was also checked using EDX in
and filtered to eliminate a colourless and insoluble the TEM microscope and in a SEM Hitachi S-4800.
powder. Finally, the product is precipitated with Samples for EDX-SEM analysis were placed in
hexane. carbon tape.

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Optical transitions Results and discussion

UV–Vis absorption spectra were recorded in transmis- Chemical composition: elemental analysis,
sion mode. In this experiment, the gold clusters and nano- ICP and EDX
particles were dispersed in liquid solutions (1 mg/mL)
of ethanol and placed into a high transmission quartz Two different types of gold nanomaterials were
cuvette; so good transmission is achieved in the UV chemically synthesized for this study: triphenylpho-
region. The spectra were collected in the range sphine-capped undecagold clusters labelled as Au11-
350–850 nm with a Shimadzu UV-2102 PC spectrom- TPP and gold nanoparticles which were named nAu-
eter at room temperature. TPP. As it will be discussed later, both particles have
a significant chlorine content coming from the
precursors AuCl(PPh3) and HAuCl4 used in the
SQUID and EPR measurements
fabrication. Across the entire synthesis process,
Teflon-coated stainless steel tools, as well as, brand
The hysteresis curves were obtained using a Quan-
new laboratory glassware were used to avoid
tum Design S6000 magnetometer at the Instituto de
unwanted effects on the magnetometry results com-
Magnetismo Aplicado in Madrid. Data were col-
ing from eventual ferromagnetic contamination.
lected at temperatures between 5 and 300 K using a
The undecagold compound was first synthesized
liquid helium cooling system. The samples were
by Bartlett et al. (1978), although there were previous
placed in adhesive kapton stuck to a quartz tube. The
theoretical studies on this system (Mingos 1976) that
diamagnetic contribution from the sample holder was
focused on various Au11 and Au13 based phosphine-
measured and subtracted from the total magnetiza-
passivated clusters. Since the synthesis method
tion. Meanwhile, the EPR measurements were
followed here claims the production of undecagold
carried out at the Instituto de Catálisis y Petroleoquı́-
gold clusters, then, despite the obtained sample could
mica in Madrid on a Bruker ER200D instrument
contain both phases (Au11 and Au13) we will refer to
operating in the X-band and interfaced to a digital
it as undecagold cluster which seems to be the most
data acquisition system. Aliquots of the studied
frequent phase. According to the literature, the result
samples were placed into a special spectroscopically
of this synthesis should be a Au11(PPh3)7Cl3 cluster
pure quartz cell. All the spectra were recorded in a
which agrees pretty well with the chemical compo-
TE104-type double cavity. The frequency of the
sition results reported in this section (cf. Table 1).
microwave was calibrated for each experiment
Regarding the phosphine-stabilized gold NPs, We-
using a standard of the stable-free radical Diph-
are et al. (2000) slightly modified the Brust method for
enylpicrylhydrazyl (DPPH) with g = 2.0036 located
thiol-capped Au NPs synthesis so phosphine-capped
in the second cavity.
gold NPs could be obtained. This method was born as
an alternative to the more complicated synthesis
X-ray absorption spectra measurements method originally formulated by Schmid et al. (1981)
which required from strictly anaerobic conditions and
XAS of the Au samples were recorded in transmis- diborane gas as a reducing agent, and resulted in 1.4 nm
sion mode at the BM29 beamline of the European Au55(PPh3)12Cl6 clusters. The NPs obtained following
Synchrotron Radiation Facility (ESRF) storage ring. Weare et al. (2000) method should have a mean size of
The samples were measured as thin self-supported 1.5 nm which according to the authors corresponds to a
pressed pellets diluted in boron nitride. Spectra were metal core of *101 gold atoms that leads to an
recorded at the Au L2- and L3-edge, at 13,734 and estimated formula of Au101(PPh3)21Cl5. However, as it
11,919 eV, respectively. Simultaneously, a gold foil will be shown later and despite having reproduced the
standard was measured to calibrate the X-ray energy. synthesis method described by Weare et al. (2000), the
To compare the X-ray absorption near-edge structure nanoparticles produced in our laboratory have a mean
region, a linear background was fitted in the pre-edge diameter of *2 nm which, according to the composi-
region and subtracted before normalization to the tional analysis performed, would lead to an estimated
edge jump. composition Au225(PPh3)80Cl16.

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Table 1 Summary of the chemical composition determined by ICP, elemental analysis and EDX (TEM and SEM), along with some
structural parameters determined from the TEM micrographs, of the phosphine-capped particles studied in this article
Sample Au Fe P C H Cl Au:P Dm SD r
(% wt)a (% wt)b (% at)c (at. ratio)d (nm) (nm)

Au11-TPP 50.1 \0.03 5.2 36.0 2.5 3.0 1.3 1.41 0.14
nAu-TPP 43.5 \0.03 5.9 41.1 2.9 3.6 3.3 2.1 0.2
a
As determined by the ICP
b
As determined by elemental analysis
c
Qualitative determination by SEM-EDX
d
As determined by TEM-EDX

Determining the exact composition of the syn- Cluster and nanoparticle topological structure
thesized samples has been proved a very difficult
task. Compositional data were obtained from induc- According to previous results, an incomplete icosa-
tively coupled plasma-atomic emission spectrometry hedral structure with an approximately C3v symmetry
analysis (ICP) for the heaviest elements (Au and Fe) axis (Bartlett et al. 1978; Nunokawa et al. 2006;
whilst the quantity of lightest elements (P, C and H) Barnard et al. 2009) is assumed for the phosphine-
was determined by elemental chemical analysis. The capped undecagold clusters which have a core diam-
results are summarized in Table 1. Unfortunately, eter of 0.8 nm. As it has already been described by
despite having performed a filtration procedure, still Menard et al. (2006b), this value is slightly overes-
some residual ligands remained free, not bonded to timated when measured by conventional bright field
any gold particle and, therefore, this led to an (BF) TEM (cf. Fig. 1). For clusters below 1 nm, the
overestimation of the gold-ligand ratio. One should poor contrast between the smallest metal NPs and the
remember that ICP and elemental chemical analysis support films used for the electron microscopy studies
provide a chemical composition quantification of the tends to bias microscopic measurements towards any
sample as a whole. Instead, energy dispersive X-ray subpopulation of larger sized particles (Narayanasw-
analysis (EDX), measured in a transmission electron amy and Marks 1993; Wilcoxon et al. 2000).
microscope (TEM), is able to quantify the chemical Meanwhile, the nAu-TPP sample with an average
composition in a very small region mainly occupied diameter of *2 nm as shown in Fig. 1, and considering
by nanoparticles which results in a more accurate a slight experimental overestimation, would correspond
determination of the gold-ligand ratio: essentially, to a bulk-like fcc structure with *225 gold core atoms,
Au:P ratio. TEM studies also allowed the size which is consistent with one of the ‘magic number’
determination of the clusters and nanoparticles. structures already reported in previous studies (Brust
However, some difficulties were found when mea- et al. 1994; Whetten et al. 1996): on the basis of X-ray
suring the Cl content in the studied samples: in diffraction (XRD) experiments recorded by Whetten at
addition to the low Cl content, the effect of a low al. (Whetten et al. 1996), a 2% expansion of the bulk
electron scattering cross section at 200 kV lead to a gold lattice constant is considered. In Fig. 2 there is a
non measurable emission line from the Cl K-shell. A perspective view diagram of the assumed models for
supplementary EDX spectrum was recorded in a both, undecagold clusters and 2 nm nanoparticles. It
different electron microscope; in this case, a 20 kV should be noted that the theoretical Au:P atomic
scanning electron microscope (SEM) where the Cl ratio shown in the nAu-TPP model nearly match the
K-shell at 2822 eV could be measured since the experimental results obtained from the EDX analysis.
electron cross section is noticeably higher at 20 kV. Despite the Au:P ratio might seem very low compared
This was used to qualitatively determine the pres- to the same ratio as calculated in the well-
ence of chlorine in the synthesized samples. The established Au55-TPP clusters, it is very similar to the
EDX results and the TEM size determination are Au:P ratio obtained for the also well-characterized
included in Table 1. [Au39(PPh3)14Cl6]Cl2 cluster (Teo et al. 1992). This

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Fig. 1 Transmission
electron micrographs of
phophine-capped Au
clusters and nanoparticles,
and their corresponding size
distribution histograms. The
solid line represents the
fitting curve assuming a
log-normal function. The
calculated mean particle
diameter (Dm) and the
standard deviation (r) are
shown in the histograms

illustrative figure provides a very good idea on how The formation of a self-assembled monolayer which, as
well-packed the PPh3 molecules must be in the NP it has been proved before (Yu et al. 2006), would have
surface, so *80 of them, along with 16 chlorine atoms, profound implications concerning the shell-core bond-
will fit in one single particle. Incidentally, regarding ing that might go beyond a plain chemisorption. A
the molecular packing structure of phenyl rings on strong bonding to the nanoparticle gold atoms will
Au(111) surfaces, it has been reported that phenyl rings deeply change the outermost surface core atoms
which usually lie flat on the gold surface when the topological structure and, subsequently, the electronic
coverage is below half-monolayer, can also adsorb structure: this point may be crucial to explain the origins
along the ring edge in stand up position to improve the of the magnetic properties.
surface coverage in saturated conditions (Müllegger Unfortunately, no additional information could be
et al. 2006). The adsorption site of PPh3 molecules and extracted from these nanoparticles and clusters by
Cl ligands is in agreement with previous structural means of high-resolution transmission electron
studies of solvated nanoparticles (Periyasamy and microscopy (HRTEM). Although valuable informa-
Remacle 2009) and conventional surface science tion has been gathered from HRTEM studies in larger
investigations (e.g. Steiner et al. 1992; Kastanas and supported nanoparticles, the application of this method
Koel 1993; Baker et al. 2008); the adsorption of to smaller clusters (D \ 3nm) is limited by image-
electronegative species are found to affect signifi- contrast, momentum-transfer, and beam-induced
cantly the gold surface structure, in particular, these mobility considerations (Cleveland et al. 1997). How-
adsorbates can lift gold atoms from the surface. The ever, the UV–Vis absorption spectra were extremely
preferred adsorption sites are surface defects such as valuable since the quality of the synthesized particles
adatoms, step edges, kinks and gold vacancies. Hence, could be checked using the absorption features. The
according to previous results by Periyasamy and UV-Vis spectra are shown in Fig. 3. The dashed line
Remacle (2009), the PPh3 molecules have been coor- corresponds to the absorption spectrum of the Au11-
dinated to the face edge atoms of the gold core outer TPP cluster which shows an absorbance feature at
layer, i.e. to the corner atoms. Meanwhile, the chlorine *420 nm typical of subnanometric phosphine-stabi-
ligands are symmetrically coordinated to the face- lized undecagold (Bartlett et al. 1978). Meanwhile, the
centred gold atoms in the sides of the nanoparticle core. solid line represents the absorption spectrum of the

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interference device (SQUID) magnetometry. The


recorded hysteresis cycles at the lowest and highest
temperature, presented in Fig. 4a and c, provided
sound information regarding the macroscopic magne-
tization of the studied systems and, clearly show the
ferromagnetic-like behaviour of the phosphine-stabi-
lized gold nanoparticles (nAu-TPP) whilst the phos-
phine-capped clusters (Au11-TPP) do not present any
magnetic feature being diamagnetic at low and high
temperature. Moreover, the magnetization versus
Fig. 2 Perspective view of the cluster and nanoparticle temperature is shown in Fig. 4b and d for samples
structure. On the left hand side panel, the subnanometric nAu-TPP and Au11-TPP, respectively. The depen-
cluster Au11-TPP with an icosahedral structure, whereas the fcc
bulklike *2 nm nAu-TPP nanoparticle is represented in the dence of the magnetization with temperature of the
right hand side panel. The gold core atoms are yellow, the red nAu-TPP sample is consistent with the observed
balls correspond to phosphorus and the green ones to chlorine. behaviour in thiol-capped gold nanoparticles (Crespo
For simplicity’s sake, the aromatic rings of the triphenylphos- et al. 2004): the hysteresis phenomenon is observed
phine molecule are not included
up to room temperature which means that this
particular system has a blocking temperature above
300 K corresponding to an anisotropy constant of
3 9 107 J m-3. Only the coercive field decreases from
850 Oe down to 300 Oe when raising the temperature
from 5 K up to room temperature. Meanwhile, the
magnetic saturation of the nAu-TPP is 0.08 lB/NP.
This value is similar to the magnetization values
associated to the Au 5d orbitals as measured with
XMCD experiments by Garitaonandia et al. (2008)
and, more recently, by de la Venta et al. (2009). The
fractional magnetization values (\1 lB) confirm that
the electron is partially shared between the surface
gold atom and the organic ligand. Since, the blocking
has its origins in the strong spin-orbit field (Hernando
et al. 2006b) then, the blocking behaviour will exist
for magnetization values well below 1 lB.
At this point an important question arises: is the
magnetic behaviour due to the existence of ferro-
magnetic and/or paramagnetic iron impurities? At the
light of the compositional results which show an iron
Fig. 3 UV–Vis absorption spectra of nAu-TPP (solid line) and content below 0.01% wt., the aforementioned possi-
Au11-TPP (dashed line) in ethanol bility sounds more than plausible. However, since the
measured Fe content is just below the detection limit
nAu-TPP nanoparticles with a broad plasmon reso- of the available chemical analysis device, then a more
nance feature at 520 nm, characteristic of *2 nm sensitive technique was needed. Here is where the
nanoparticles (Alvarez et al. 1997). electron paramagnetic resonance spectroscopy comes
into play. This technique is able to detect very low
Magnetic behaviour: SQUID and EPR quantities of chemical species that have one or more
measurements unpaired electrons. Therefore, the EPR results will
provide information on the presence of magnetic
The magnetic behaviour of the systems presented here impurities and also on their magnetic state. These
was studied by means of superconducting quantum results are shown in Fig. 5. The spectra were

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(a) (c)

(b) (d)

Fig. 4 SQUID magnetometry results. Panels in the left-hand 5 and 300 K. Meanwhile, bottom panels show the thermal
side correspond to the nAu-TPP sample and panels in the right- dependence of the magnetization under an applied magnetic
hand side are the results obtained from the subnanometric field of 500 Oe: figures b and d correspond to samples nAu-
cluster Au11-TPP. Figures a and c contain the magnetization TPP and Au11-TPP, respectively. The inset in figure (a) shows
curves from nAu-TPP and Au11-TPP, respectively, measured at a magnification of the hysteresis curve between -1 to 1 k Oe

recorded at 77 and 298 K. The almost featureless 8000 gauss in both spectra, there are spiky peaks
EPR signals suggest that there are not magnetic iron which correspond to paramagnetic O2 molecules that
impurities in any of the studied samples; in particular, were in the analysis chamber due to pressure
according to Jiang et al. (2002) if Fe3? impurities conditions, slightly higher than the ones set at
were present an intense peak around 1,600 gauss (g = 298 K. The EPR results are very useful to rule out
4.28 at crossover point) should appear in the EPR any potential contribution of magnetic iron impurities
spectrum. The only remarkable feature can be found to the measured hysteresis cycles. Thus, the ferro-
in the spectra recorded from the nAu-TPP sample, magnetic-like behaviour of the nAu-TPP sample must
which presents a broad peak at low g values (g * 2.1 have its origins somewhere else.
or B * 3000 Oe). This feature that is observed at
both high and low temperatures increases its line- Electronic structure
width and shifts towards higher g values at low
temperature which is a characteristic behaviour of Another point to be explored is an eventual polari-
ferromagnetic centres (Tronconi et al. 1993; Fittip- zation of the Au–P and Au–Cl bonds. Here, the X-ray
aldi et al. 2009) such as our phosphine-capped gold absorption spectroscopy (XAS) experiments have
nanoparticles. Finally, at 77 K, between 5000 and been very valuable. In particular, the X-ray

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according to the XANES results reported in this


article where subnanometric phosphine-protected
gold clusters present a noticeably large charge
transfer in the Au-ligand bond and, according to the
SQUID experiments on the very same clusters where
a diamagnetic behaviour is observed, then the charge
transfer effect can be ruled out as the only responsible
effect of the ferromagnetic-like character. This claim
is reinforced if the charge transfer of the nAu-TPP is
considered. In this case, the measured resonance of
the XANES edge is significantly less intense than in
the Au11-TPP sample and, in spite of this, the
ferromagnetic-like character appears in the nanopar-
ticles whilst it is not observed in the subnanometric
clusters. Recently, Walter et al. (2008) have per-
formed density functional theory calculations of
structurally characterized ligand-protected gold clus-
ters and nanoparticles. As a result, their determina-
tion of the electronic structure, i.e. d-hole generation,
agrees with the magnetic behaviour previously
observed in thiol-capped gold NPs (Crespo et al.
2006). Walter et al. (2008) also claim that, in the
Au11(PPh3)7Cl3 clusters, the phosphine ligands are
weak surfactants that cannot significantly modify the
electron shell structure of the gold cluster core and, it
would be the chlorine ligand the one that plays the
Fig. 5 Electron paramagnetic resonance spectra from the
studied samples: nAu-TPP upper panel and Au11-TPP bottom role of the thiol ligand in the aforementioned
panel. Data were collected at T = 298 and 77 K. In both magnetic nanoparticles (Crespo et al. 2006). In our
samples, spiky features appear between 5,500 and 8,000 gauss case, the strong charge transfer observed from the
magnetic fields in the EPR spectra taken at 77 K; these XANES spectrum of the undecagold clusters might
correspond to molecular oxygen present in the analysis
chamber due to vacuum conditions slightly higher than the be solely attributed to the Au–Cl bond. Unfortu-
typical base pressure nately, the data presented in this research work are
not able to discern whether the major charge transfer
absorption near-edge structure (XANES) data of the effect is due either to phosphine or chlorine ligands.
Au-L3 edge, which have a first resonance around The presence of possible individual Au?-species has
5 eV above the threshold energy (whiteline) associ- not been detected by EPR. However, regardless of
ated with a 2p3=2 ! 5d5=2;3=2 dipole transition that what is the exact relative number of Au–P and Au–Cl
is actually probing the density of unoccupied d states bonds, it seems to be very clear that a balance
at the Fermi level (Zhang and Sham 2002). Despite between Au-ligand charge transfer and Au–Au bond
gold should have a nominally full 5d band, due to s- is indeed necessary in order to originate a net
p-d hybridization, a faint whiteline is still detected magnetic moment. This balance as observed from
for bulk gold (cf. Fig. 6). The area under the XANES the XANES whiteline represents a slight charge
curve will provide an accurate estimation on the transfer large enough to originate a strong electric
charge redistribution, i.e. a charge transfer phenom- dipole along the bond but, at the same time, weak
enon taking place in the gold-ligand bond. As it has enough to keep the metallic character of the inner
been previously discussed, the charge transfer effect gold atoms in the nanoparticle core. The optimum
that occurs in the Au–S bond of the thiol-capped gold balance has been found for the thiol-capped gold NPs
NPs is an essential point to explain the origins of the synthesized following the Brust method and also for
magnetic behaviour. However, considering that the nAu-TPP NPs.

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1316 J Nanopart Res (2010) 12:1307–1318

arrangement of the charge dipoles formed at the Au-


ligand bond and, consequently, the nanoparticle
surface electrons would collectively move along the
domain boundaries. The coexistence of a collective
electron movement that leads to a weak surface
plasmon resonance and some degree of mobility is a
key point in the appearance of a permanent magnetic
moment (Hernando et al. 2006a). The well-ordered
structure of the capping system, far from ideal, is a
more than possible situation. In fact, a close-packed
layer is the only way to explain such a high number
of ligands: *80 PPh3 molecules and 16 Cl atoms for
a given nanoparticle, as it has been determined by the
chemical composition study.

Conclusions

In summary, the existence of a permanent magnetic


Fig. 6 Au L3-edge XANES spectra of the the synthesized behaviour in phosphine-chlorine-capped gold nano-
samples: nAu-TPP and Au11-TPP, compared with bulk Au and
the polymeric precursor Au(PPh3)Cl used in the cluster
particles has been shown for the first time by means
synthesis of SQUID magnetometry. The EPR experiments
confirm that Fe3? species are not present in the
samples; therefore, the origins of the observed
Beyond this argument, there is a point to be ferromagnetic behaviour must be somewhere else.
considered yet: the electronic structure of the system These results agree with previous investigations on
as a whole. As it has been previously investigated thiol-capped gold nanoparticles carried out using
(Bartlett et al. 1978; Yang and Chen. 2003; Menard XMCD and Mössbauer spectroscopy. The peculiar
et al. 2006a), the phosphine-capped gold clusters magnetic behaviour does not have its origins in one
have a molecule-like electronic structure which single factor; instead, there are several factors that
presents almost discrete electron energy levels below contribute to the appearance of a permanent magnetic
500 nm in the UV–visible absorption range. Instead, moment. One factor is a charge transfer effect
the electronic structure of the phosphine-capped gold occurring at the Au-ligand bond which must be
NPs presents a broad plasmon feature around linked to the presence of Au–Au bonds that provide a
520 nm. This particular behaviour is due to the metallic character: this is the reason that explains the
presence or not of metallic Au–Au bonds in the diamagnetic behaviour of phosphine-chlorine-capped
system; the surface plasmon resonance feature is clusters, where there is very probable that the Cl
strongly marked for gold particles above 10 nm anions are dominating the charge transfer pulling the
which have an almost metallic character. The pres- electrons towards the ligand and, therefore limiting
ence of adsorbates in the nanoparticle surface, the mobility of the nearby electrons that finally
namely PPh3 molecules, which reduce the surface vanishes any chance of generating an orbital mag-
electrons mobility would significantly damp the netic moment. Additionally, the EPR spectra also
surface plasmon resonance as it has already been show a faint peak at low g values in the nAu-TPP
proved (Guerrero et al. 2008). However, if the sample which could be attributed to the ferromagne-
adsorbate molecules, in this case phosphine and tism observed in these nanoparticles. Finally, the self-
chlorine ligands, form a well-ordered and close- assembling of an ordered capping layer is also a key
packed structure then, small domains of ordered PPh3 factor since the formation of charge dipole domains
molecules and Cl atoms could self-assemble in the will drive the movement of the surface electrons that
nanoparticle core facets. This would finally lead to an finally lead to the appearance of a magnetic moment.

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J Nanopart Res (2010) 12:1307–1318 1317

Acknowledgements The authors would like to acknowledge smaller gold nanocrystals: the truncated decahedral motif.
the support of the European Synchrotron Radiation Facility and Phys Rev Lett 79(10):1873–1876
BM29 beamline staff. This research has been supported by the Crespo P, Litrán R, Rojas TC, Multigner M, de la Fuente JM,
Spanish Ministry of Science ‘Ministerio de Ciencia e Innovación Sánchez-López JC, Garcı́a MA, Hernando A, Penadés S,
(MICINN)’ (Strategic Action NAN2004-09125-C07) and the Fernández A (2004) Permanent magnetism, magnetic
Andalusian Government ‘Junta de Andalucı́a’ (Excellence anisotropy, and hysteresis of thiol-capped gold nanopar-
Project P06-FQM-02254 and P09-FQM-4554, group TEP127). ticles. Phys Rev Lett 93(8):87, 204
M.A. Muñoz-Márquez thanks the Spanish Research Council Crespo P, Garcı́a MA, Fernández-Pinel E, Multigner M, Al-
‘Consejo Superior de Investigaciones Cientı́ficas (CSIC)’ I3P cántara D, de la Fuente JM, Penadés S, Hernando A
programme, E. Guerrero acknowledges the MICINN for (2006) Fe impurities weaken the ferromagnetic behavior
financial support and R. Lucena thanks CSIC for a PhD grant. in Au nanoparticles. Phys Rev Lett 97(17):177, 203
Daniel MC, Astruc D (2004) Gold nanoparticles: assembly,
supramolecular chemistry, quantum-size-related proper-
ties, and applications toward biology, catalysis and
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