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2D assembly of non-interacting magnetic iron oxide nanoparticles

via click chemistryw
Delphine Toulemon,a Beno t P. Pichon,*a Xavier Cattoen,b Michel Wong Chi Manb and
Sylvie Begin-Colina
Received 29th July 2011, Accepted 12th September 2011
DOI: 10.1039/c1cc14661k
Azide-terminated magnetic iron oxide nanoparticles have been
assembled in 2D on alkyne-terminated self-assembled monolayers
(SAMs) by the copper(I) catalyzed alkyneazide cycloaddition
(CuAAC) click reaction; the kinetics of the reaction is an
important parameter to control the interparticle distance and
thus the dipolar interactions.
Magnetic nanoparticle (NP) assemblies have attracted a
tremendous attention due to their potential applications such
as recording media or nanosensors.1,2 Because the magnetic
collective properties of such nanostructures are strongly
dependent on the spatial arrangement of NPs,3 self-assembly
methods4 such as the LangmuirBlodgett,5 the self-induced
evaporation6 and the Layer-by-Layer7 techniques have been
widely investigated. The collective magnetic behaviour of FePt
NP assemblies has also been demonstrated to depend on the
NP surface chemistry.8 Recently, 2D molecular nanopatterns
consisting in self-assembled monolayers (SAMs) of organic
molecules were shown to address the assembling of iron oxide
NPs in sizeable domains through specic interactions.9,10
Although these methods produce well-dened nanostructures,
NPs are usually assembled through weak interactions with the
surface and may rearrange as a result of interparticle interactions.10 Hence controlling the interparticle distance in 2D
assemblies is not a trivial issue and requires new approaches
allowing the stable anchoring of NPs on substrates.
Previously reported as a very ecient way to functionalize
various types of NPs for a wide range of applications, the
copper(I) catalyzed alkyneazide cycloaddition (CuAAC)
click reaction11,12 is now opening new opportunities to
address NP assembling. Owing to its high selectivity, versatility and easy process, highly stable NP assemblies have been
built through the irreversible formation of covalent bonds
a

Institut de Physique et de Chimie des Materiaux de Strasbourg,

UMR 7504, CNRS-UdS-ECPM, 23 rue du Loess, BP 43, F-67034
Strasbourg Cedex 2, France. E-mail: Benoit.Pichon@unistra.fr;
Fax: +33 (0)3 88 10 72 47; Tel: +33 (0)3 88 10 71 33
b
Institut Charles Gerhardt Montpellier, UMR 5253, CNRS-UM2ENSCM-UM1, 8 rue de lecole Normale, 34296 Montpellier Cedex
5, France
w Electronic supplementary information (ESI) available: SEM, TEM,
HRTEM micrographs, electron diraction patterns, FTIR and PMIRRAS spectra and magnetic measurements. See DOI: 10.1039/
c1cc14661k

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Chem. Commun., 2011, 47, 1195411956

such as 1D arrangement directed by DNA13 or as sizeable

assemblies combining quantum dots and magnetic NPs.14
FePt NPs have also been assembled on SAMs through micropatterning which resulted in an enhanced magnetocrystalline
anisotropy.15
In this article, the 2D assembling of magnetic iron oxide
NPs with controlled interparticle distance is addressed by the
CuAAC click reaction. Azide-terminated NPs were immobilized by reaction with alkyne-terminated SAMs. The NP
density on the SAM being dependent on the kinetics of the
reaction, their assembling has been easily patterned as a
function of the reaction time. On this basis, the interparticle
distance has been tuned and its inuence on the magnetic
collective properties induced by dipolar interactions between
NPs has been investigated. Furthermore we succeeded in
obtaining a 2D array of quasi non-interacting magnetic NPs.
The synthesis of azide functionalized iron oxide NPs was
performed according to the following two-step procedure.
Firstly, 11 nm-sized iron oxide NPs coated with oleic acid
(NP@OA) were synthesized by the thermal decomposition of
iron stearate (Fe(stea)2) in octyl ether used as a high boiling
temperature solvent (bp 288 1C) (see ESIw).1618 Secondly,
owing to the weak interaction between carboxylic acid groups
and the NP surface,9 the direct exchange of oleic acid by an
azidoalkyl-phosphonic acid (2-azidoethyl- or 12-azidododecyl
phosphonic acid (AP2 or AP12)) was easily performed. The
strong interaction between the phosphonic acid groups and
the NP surface19,20 yielded azide functionalized NP@AP2 and
NP@AP12. Spherical NPs with a narrow size distribution
(11.1  1.2 nm) were obtained as shown by TEM (Fig. 1a,c).
The ligand exchange proceeded in THF for NP@AP12,
whereas, according to the short ethylene chains and the
polarity of azide groups of AP2, a THF/DMF mixture
(v : v, 9 : 1) was needed to ensure the stability of the NP@AP2
suspension. Highly stable suspensions were obtained as shown
by granulometry measurements (Fig. 1b,d). The decrease of
the mean hydrodynamic diameter of both NP@AP2 (11.2 
2.1 nm) and NP@AP12 (12.3  2.5 nm) in comparison to
NP@OA (13.0  2.1 nm) fully agrees with the shorter alkyl
chains of AP2 and AP12. The eciency of the direct exchange
was also characterized by FTIR spectroscopy (see ESIw). Both
spectra of NP@OA and NP@AP12 show nFeO (589 cm 1)
and nCH2 bands (2918 and 2849 cm 1) corresponding to iron
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Scheme 1 Schematic representation of covalent assembling of azideterminated NPs on alkyne-terminated SAMs by the CuAAC click
reaction.

Fig. 1 TEM micrographs (a, c), DLS and TEM size distribution for
NP@AP2 (a, b) and NP@AP12 (c, d).

Chart 1 Reaction pathway to obtain 11-(undec-1-ynyl)thioacetate

(HCC(CH2)9SCOCH3). (a) ClSO2CH3, Et3N, RT, 2 h. (b) KSCOCH3,
reux under N2, 3 h.

oxide and alkyl chains, respectively. The disappearance of the

characteristic nCO band of oleic acid (1635 cm 1) and of the
nasCH3 band (2956 cm 1) in the NP@AP12 spectrum and the
appearance of nN3 (2096 cm 1) band agree with the replacement of oleic acid by AP12 at the NP surface. In addition, the
interaction of the phosphonic acid group with the NP surface
was evidenced by the appearance of a broad nPOFe band
(1200900 cm 1).19 The disappearance of the nPOH bands
(1101 and 945 cm 1) and the observation of a shoulder at 1106 cm 1
corresponding to the nPQO band of AP12 suggest a binulcear
bridging complex.
Alkyne-terminated self-assembled monolayers (SAMs) were
prepared by immersing a gold substrate in a 10 mM ethanolic
solution of 11-(undec-1-ynyl)thioacetate for 15 h according to
the standard solution procedure.21 Thioacetates were used
because of the low stability of the corresponding alkynethiol
derivative. Indeed, thiol and alkyne react easily to form CS
bonds in a similar manner to the thiol-ene reaction.22 To
overcome this drawback, 11-(undec-1-ynyl)thioacetate was
prepared starting from the 11-undec-1-yn-11-ol through a
methylsulfonate intermediate (Chart 1) on the basis of a
synthesis pathway described by Collman et al.23 The
formation of alkyne-terminated SAMs is accompanied by
the observation of intense nCH bands (29502850 cm 1) in
the PM-IRRAS spectrum although the very weak nCC band is
not observed. In addition, the presence of sulfur-containing
fragments bonded to gold was evidenced by XPS which
exhibits the S(2p) signal at 163.5 eV.
The azide-terminated NPs were assembled on alkyne-terminated SAMs under non-aqueous conditions via the CuAAC
click reaction (Scheme 1) as we reported previously on the
synthesis of silane derivatives.24,25 Alkyne-terminated SAMs
were immersed in NP suspensions containing EtN3 and
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Fig. 2 SEM pictures of SAM-1h (a) and SAM-48h (b) after the
CuAAC click reaction.

CuBr(PPh3)3 as catalyst. The reaction was performed under

reux for 1 h with NP@AP2 and 48 h with NP@AP12. Both
samples SAM-1h and SAM-48h were then extensively rinsed
and ultrasonicated to remove physisorbed NPs. As seen by
SEM (Fig. 2), the NP density increases with the reaction time
from 530 to 2005 NPs per mm2, which conrms the inuence of
the kinetic control over the assembling process. Because NPs
cover homogeneously both SAMs, the average interparticle
distance is reduced on increasing the reaction time from 1 to
48 h. A blank experiment was performed for 48 h by using a
methylene-terminated SAM on which no particles were
assembled (see ESIw). This demonstrates the selectivity of
the click reaction to pattern NP assemblies.
The magnetic properties of both samples were studied by
using a superconducting quantum interference device
(SQUID) magnetometer (Fig. 3a). Zero-eld-cooled (ZFC)
magnetization curves of SAM-1h and SAM-48h exhibit a
maximum at 80 K and 145 K, respectively. This is generally
associated to the blocking temperature (TB) which is the
temperature limit between the single blocked monodomain
behaviour (T o TB) and the superparamagnetic behaviour
(T 4 TB) of NPs. The signicant increase of TB with the
density and the average interparticle distance is clearly correlated
to the increase of dipolar interactions as reported previously
on similar iron oxide NPs dispersed in solution.26 The increase
of dipolar interactions is also depicted by the broadening of
the ZFC curve related to SAM-48h.10a Moreover, the eldcooled (FC) magnetization curves exhibit dierent behaviours
at temperatures below TB that are also related to the strength
of dipolar interactions between NPs. SAM-48h presents a
plateau which is typical of strong dipolar interactions between
NPs.16 In contrast, the gradual increase of the magnetization
Chem. Commun., 2011, 47, 1195411956

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We are grateful to the Agence Nationale de la Recherche

(ANR) and the Direction Generale de lArmement (DGA) for
nancial supports. P. Fioux from IS2M in Mulhouse is
thanked for XPS analyses.

Notes and references

Fig. 3 (a) ZFC and FC curves and (b) M(H) curves (in-plane and
out-of-plane measurements) at 5 K, for SAM-1h and SAM-48h.

for SAM-1h is ascribed to weak dipolar interactions and is

correlated to larger interparticle distances.10a
The magnetization of both samples versus an applied eld
was also studied at 5 K and 300 K (see ESIw). Magnetic
hystereses were observed for both samples at 5 K (below TB)
whereas at 300 K (above TB), the curves perfectly overlap.
It is typical of the ferrimagnetic and superparamagnetic
behaviours, respectively, of such 11 nm-sized iron oxide NPs.16
More interestingly, the inuence of the interparticle distance
on the magnetic anisotropy of NP assemblies can be determined at 300 K by applying a eld in a direction parallel
(in-plane) and perpendicular (out-of-plane) to the lm
(Fig. 3b). The magnetization reaches faster the saturation for
in-plane than for out-of-plane measurements on SAM-48h.
A short interparticle distance favours strong dipolar interactions
which result in the preferential alignment of magnetic
moments in-plane as already reported on dense lms of
magnetic NPs.3,7 In contrast, no signicant dierence between
in-plane and out-of-plane measurements was observed for
SAM-1h. Indeed, large interparticle distances disfavour dipolar
interactions and individual NP magnetic moments proceed
with random orientation in space. Magnetic moments align
along the direction of the eld with no competition prior to
dipolar interactions.
In summary, for the rst time, the CuAAC click reaction
is reported to control the assembling and the magnetic properties
of iron oxide NPs. This approach results in the control of the
interparticle distance within 2D assemblies by taking advantage
of the functionality of NPs, the irreversibility and the kinetics
of the reaction. Short interparticle distances result in strong
dipolar interactions between NPs which occur preferentially in
the plane of the lm. In contrast, large interparticle distances
lead to individual NPs featured by randomly oriented
magnetic moments and weak dipolar interactions. To the best
of our knowledge, it is the rst time that quasi non-interacting
magnetic nanoparticles are assembled in 2D by the click
reaction. The presented method may also be applied to other
types of functionalized NPs to address their physical
properties.

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Chem. Commun., 2011, 47, 1195411956

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