Organometallics 2009, 28, 5341–5348 5341

DOI: 10.1021/om900375x

Surface Modification of Fe3O4 and FePt Magnetic Nanoparticles with

Organometallic Complexes
Sang Bok Kim, Chen Cai, Jaemin Kim, Shouheng Sun, and Dwight A. Sweigart*
Department of Chemistry, Brown University, Providence, Rhode Island 02912

Received May 11, 2009

Hexane solutions of Fe3O4 and FePt nanoparticles (NPs) having both oleylamine and oleic acid as
surfactants were surface modified by treatment with a DMSO solution of [(η6-hydroquinone)-
Mn(CO)3]BF4, which is readily deprotonated by the oleylamine to [(η5-semiquinone)Mn(CO)3]. The
latter complex binds to the NP by replacing the protonated oleylamine, which likely forms a bilayer
with the alkyl chains of the oleic acid on the NP surface. The resulting surface-modified assembly is
soluble in DMSO. With FePt nanoparticles, [(η5-semiquinone)Mn(CO)3] coordinates to the Pt atoms
and the IR frequency of the tricarbonyls differs from that obtained with Fe3O4 nanoparticles, in
which coordination is to the iron.

1. Introduction complexes are employed. Magnetic nanoparticles are good

candidates for a catalyst immobilization support because
Materials at the nanometer scale have been studied for their magnetic properties allow facile catalyst separation.
decades because of their unique properties arising from the In addition, nanoparticles do not suffer from porosity and
large fraction of atoms that reside on the surface and the associated problems with reactant/product transport
correspondingly finite number of atoms in the crystalline to/from the catalyst (e.g., as in MCM-41).8
core. Research on metallic (e.g., Au) and semiconductor Many chemical routes for the synthesis of nanoparticles
(e.g., CdSe, ZnSe, CdTe) nanoparticles (NPs) has been rely on varying the type and concentration of the surfactants
increasingly focused on the dependence of the chemical in order to tune the size of the nanoparticles obtained.
and physical properties on size and shape, which in turn Usually, nanoparticles are protected against oxidation and
dictates potential applications in catalysis, sensors, and aggregation by a layer of surfactant molecules, which make
molecular electronics.1 Chemically synthesized magnetic them soluble in nonpolar solvents and unstable in polar
nanoparticles have drawn much attention due to their unique solvents. The polar heads of the surfactant molecules bind
properties that derive from the small particle size and uni- to the surface of the nanoparticles, and the nonpolar tails of
form size distribution.2 Due to their small size, almost all the surfactants are soluble in nonpolar solvents. The insolu-
magnetic nanoparticles are superparamagnetic; such materi- bility of many nanoparticles in polar solvents can restrict
als are intrinsically nonmagnetic in the bulk but can be their use in, for example, biomedical applications. To make
readily magnetized in the presence of an external field.3,4 nanoparticles soluble in water and other polar solvents, two
Superparamagnetic iron oxide nanoparticles with suitable methods are generally employed. One method is bilayer
biocompatible coatings have been used in biomedical appli- formation when a long-chain polar surfactant interdigitates
cations such as magnetic resonance imaging (MRI) contrast with the surfactant hydrocarbon tails around the nanopar-
enhancement, tissue engineering, and drug delivery.5 ticles and provides a positive surface charge. For example,
Immobilization of homogeneous catalysts on various dodecylamine-capped gold nanoparticles dispersed in
support materials such as organic polymers,6 inorganic chloroform have been transferred into water using cetyltri-
silica, and metal oxides (such as Al2O3)7 has been investi- methylammonium bromide. A second method involves li-
gated as a means to recover and recycle the catalysts, gand exchange3,9 in which an excess of a ligand is added to
especially when expensive and/or toxic heavy metal the nanoparticle solution. The ligand has both a functional
group (e.g., thiol) at one end that can displace the original
*Corresponding author. E-mail: [email protected]. ligand on the nanoparticle surface and a polar tail or polar
(1) Merkoc-i, A. FEBS J. 2007, 274, 310.
(2) Salgueiri~no-Maceira, V.; Liz-Marzan, L. M.; Farle, M. Langmuir
functional group at the other end.10,11 Highly monodisperse
2004, 20, 6946–6950.
(3) Bagaria, H. G.; Ada, E. T.; Shamsuzzoha, M.; Nikles, D. E.; (8) Yoon, T.-J.; Lee, W.; Oh, Y.-S.; Lee, J.-K. New J. Chem. 2003, 27,
Johnson, D. T. Langmuir 2006, 22, 7732–7737. 227–229.
(4) Hu, A.; Yee, G. T.; Lin, W. J. Am. Chem. Soc. 2005, 127, 12486– (9) Dubios, F.; Mahler, B.; Dubertret, B.; Doris, E.; Mioskowski, C.
12487. J. Am. Chem. Soc. 2007, 129, 482–483.
(5) Yang, T.; Shen, C.; Li, Z.; Zhang, H.; Xiao, C.; Chen, S.; Xu, Z.; (10) Choi, J.-S.; Jun, Y.-W; Yeon, S.-I.; Kim, H. C.; Shin, J.-S.;
Shi, D.; Li, J.; Gao, H. J. Phys. Chem. B 2005, 109, 23233–23236. Cheon, J. J. Am. Chem. Soc. 2006, 128, 15982–15983.
(6) Yoo, D.-W.; Han, J.-H.; Nam, S. H.; Kim, H. J.; Kim, C.; Lee, (11) Palma, R. D.; Peeters, S.; Bael, M. J. V.; Rul, H. V. D.; Bonroy,
J.-K. Inorg. Chem. Commun. 2006, 9, 654–657. K.; Laureyn, W.; Mullens, J.; Gustaaf, B.; Guido, M. Chem. Mater.
(7) Wang, Y.; Lee, J.-K. J. Mol. Catal. A: Chem. 2007, 263, 163–168. 2007, 19, 1821–1831.

r 2009 American Chemical Society Published on Web 09/02/2009 pubs.acs.org/Organometallics

5342 Organometallics, Vol. 28, No. 18, 2009 Kim et al.

magnetic nanoparticles are commonly prepared via thermal growth of Au nanoparticles from FePt nanoparticle
decomposition of organometallic compounds in the presence seeds.10
of oleic acid and oleylamine, which serve as surfactants and
permit good control of size, shape, composition, and internal 2. Experimental Section
structure.12,13
In this paper, we present a study of magnetic nanoparticles Ligand-Exchange Procedures. The Supporting Information
stabilized with oleylamine and oleic acid. In particular, should be consulted for details not provided here. The ligand
selective displacement of oleylamine from the surface of exchange of the as-made 10 nm Fe3O4 nanoparticles with [(η6-
nanoparticles having both oleyamine and oleic acid as hydroquinone)Mn(CO)3]BF4 and [(η6-C6H5OH)Mn(CO)3]BF4
surfactants is demonstrated. The displacement of the oleyl- was carried out as follows. Approximately 20 mg of Fe3O4
amine was achieved by combining a hexanes solution of the nanoparticles in 2 mL of hexane was mixed with 40 mg of [(η6-
hydroquinone)Mn(CO)3]BF4 in 2 mL of DMSO in a 10 mL vial.
NP and a DMSO solution of [(η6-hydroquinone)Mn(CO)3]- The mixture formed two layers. The upper layer contained the
BF4. The Mn complex is readily deprotonated by the oleyl- Fe3O4 nanoparticles, and the lower layer contained the organo-
amine to generate [(η5-semiquinone)Mn(CO)3] (SQMTC: metallic complex. After 3 h shaking, all of the nanoparticles in
semiquinone manganese tricarbonyl). The surface sites gen- the hexane layer had transferred to the DMSO layer. To remove
erated by the protonation of the oleylamine in this manner excess organometallic complexes used in this process, the
are then occupied by coordination of [(η5-semiquinone)Mn- DMSO solution was put into fresh THF. The NP precipitate
(CO)3] and DMSO to the metal. The NP modified in this way was collected by a magnet and washed with fresh THF. The
is soluble in DMSO. The [(η5-semiquinone)Mn(CO)3] binds precipitate is soluble in polar solvents (DMSO and acetone) and
to the NP via coordination of a quinone oxygen atom. IR insoluble in comparatively nonpolar solvents (THF, dichloro-
spectra in the carbonyl region can be used to follow the methane, hexane, and so on). The ligand exchange of the as-
made FePt nanoparticles with organometallic complexes was
coordination. It was observed that the IR bands of the carried out by the same method as with Fe3O4 nanoparticles
tricarbonyls depend on the metal. Thus, when [(η5-semiqui- except that centrifugation was used for the isolation of the
none)Mn(CO)3] is coordinated to Fe on the surface of Fe3O4 ligand-exchanged NPs.
nanoparticles, the IR bands are at higher frequencies than Characterization. The FePt nanoparticles and Fe3O4 nano-
when coordination is to Pt on the surface of FePt nano- particles were characterized by transmission electron micro-
particles. scopy (TEM, Philip EM 420 at 120 kV and JEOL2010 at
Most ligand exchanges on the surface of nanoparticles 200 kV). The Fe and Pt compositions were measured by
having both oleylamine and oleic acid as surfactants have energy-dispersive X-ray spectroscopy (EDX). X-ray powder
been accomplished by two modes:3,10,14 (i) exchange of diffraction patterns of the samples were collected on a Bruker
oleylamine by a stronger field ligand (ligand exchange of AXS D8-Advanced diffractometer with Cu KR radiation (λ =
1.5418). Fourier transform infrared (FTIR) spectra of the FePt
oleylamine by dodecanethiol, of oleic acid by a catechol nanoparticles and Fe3O4 nanoparticles before and after the
group of dopamine, and of both oleylamine and oleic acid by phase transfer were collected via KBr disks. The particles were
dihydrolipoic acid, and so on); (ii) ligand exchange by precipitated from solution, dried under vacuum, mixed with
ligands having a similar ligand field strength (ligand ex- KBr, and compressed into pellets. The nanoparticles were
change of oleic acid by the carboxylic end of mercaptoun- deposited from their (DMSO and hexane) dispersions on either
decanoic acid, of poly(ethyleneglycol)-terminated thiol by an amorphous carbon-coated copper grid for TEM image
ammonium-terminated PEG-thiol, and so on). Herein it is analyses or a Si substrate for XRD analyses.
shown that weaker field ligands such as [(η5-semiqui-
none)Mn(CO)3] and DMSO can displace oleylamines on 3. Results and Discussion
the surface of the nanoparticle by a coupled protonation of
the oleylamine. The importance of the protonation step The as-made Fe3O4 nanoparticles are soluble in hexane
is shown by the observation that the anionic complex due to the presence of oleic acid and oleylamine surfactants.
[(η4-quinone)Mn(CO)3]- (QMTC: quinone manganese They are insoluble in DMSO. Even after 2 h shaking,
tricarbonyl) fails to directly replace oleylamine on the sur- there was no transfer of nanoparticles from the hexane
face of Fe3O4 nanoparticles. layer to the DMSO layer (Figure 1a). This means that there
[(η5-Semiquinone)Mn(CO)3] has been used for making is no change at the surface of the nanoparticles. Fe3O4
organometallic coordination polymers.15-17 [(η5-Semiqui- nanoparticles in hexane and [(η6-hydroquinone)Mn(CO)3]-
none)Mn(CO)3] on the surface of a Fe3O4 nanoparticle can BF4 in DMSO were combined (Figure 1b) and shaken
be switched to [(η4-quinone)Mn(CO)3]- and consequently for 2 h. The Fe3O4 nanoparticles in hexane transferred
initiate the formation organometallic coordination net- to the DMSO layer (Figure 1c). It was thought likely that
works. In this manner, [(η5-semiquinone)Mn(CO)3] bound the protons from [(η6-hydroquinone)Mn(CO)3]BF4 play a
to Fe3O4 nanoparticles functions as a seed for organometal- role in the transfer. [(η6-Hydroquinone)Mn(CO)3]BF4 is
lic coordination polymer formation, in analogy to the much more acidic (pKa ca. 3) than hydroquinone itself
(pKa ca. 10) because the Mn(CO)3þ moiety withdraws
(12) Sun, S. Adv. Mater. 2006, 18, 393–403. electron density. In fact, [(η6-hydroquinone)Mn(CO)3]BF4
(13) Sun, S.; Zeng, H.; Robinson, D. B.; Raoux, S.; Rice, P. M.; equilibrates to [(η5-semiquinone)Mn(CO)3] þ HBF4 in
Wang, S. X.; Li, G. J. Am. Chem. Soc. 2004, 216, 273–279. DMSO (Scheme 1).
(14) Hong, R.; Fischer, N. O.; Emrick, T.; Rotello, V. M. Chem.
Mater. 2005, 17, 4617–4621.
To test the role of acid, [(η6-dimethoxybenzene)Mn-
(15) Oh, M.; Carpenter, G. B.; Sweigart, D. A. Acc. Chem. Res. 2004, (CO)3]BF4 was synthesized because this complex has a
37, 1–11. similar molecular structure to [(η6-hydroquinone)Mn-
(16) Reingold, J. A.; Jin, M.; Sweigart, D. A. Inorg. Chim. Acta 2006, (CO)3]BF4 but has no acidic protons. The former complex
359, 1983.
(17) Oh, M.; Carpenter, G. B.; Sweigart, D. A. Angew. Chem., Int. Ed. is soluble in DMSO, but did not induce transfer of Fe3O4
2003, 42, 2025. nanoparticles to DMSO (Figure 1d).
Article Organometallics, Vol. 28, No. 18, 2009 5343

Figure 1. (a) Fe3O4 NPs in hexane and pure DMSO were combined and shaken for 2 h, (b) [(η6-hydroquinone)Mn(CO)3]BF4 in
DMSO and Fe3O4 NPs in hexane, (c) after (b) was shaken, (d) [(η6-dimethoxybenzene)Mn(CO)3]BF4 (30 mg) in DMSO and Fe3O4 NPs
(10 mg) in hexane were combined and shaken for 2 h, (e) HBF4 (4 μL) in DMSO and Fe3O4 NPs (10 mg) in hexane were combined, (f) (e)
was shaken for 2 h, (g) p-nitrophenol (20 mg) in DMSO and Fe3O4 NPs in hexane were combined and shaken for 2 h, (h) formic acid (2
μL) in DMSO and Fe3O4 NPs (10 mg) in hexane were combined and shaken for 2 h, (i) phosphoric acid (4 μL) in DMSO and Fe3O4 NPs
(10 mg) in hexane were combined and shaken for 2 h, (j) oleylammonium-BF4- in DMSO and Fe3O4 NPs in hexane were combined and
shaken for 2 h, (k) NH4þBF4- (30 mg) in DMSO and Fe3O4 NPs (10 mg) in hexane were combined and shaken overnight, (l) TBABF4
(30 mg) in DMSO and Fe3O4 NPs (10 mg) in hexane were combined and shaken for 2 h, (m) [(η6-dimethoxybenzene)Rh(COD)]BF4 (30
mg) in DMSO and Fe3O4 NPs (10 mg) in hexane, (n) after (l) was shaken for 2 h.

Scheme 1. Two Applications of [(η6-Hydroquinone)Mn(CO)3]BF4 (pH curve in 1:1 MeCN and water); (1) Acid-Promoted Decoordina-
tion of Oleylamine from the Nanoparticle Surface to Generate Free Coordination Sites and (2) Formation of Organometallic Coordination
Polymers

To further test the effect of acid, HBF4, p-nitrophenol, experiment, it can be expected that phosphoric acid
formic acid, and phosphoric acid were chosen. Only HBF4 (pKa = 2.12) would induce transfer. However, this did
acid (4 μL, pKa = -4.9) led to nanoparticle transfer to not happen (Figure 1i), and when excess phosphoric acid
DMSO (Figure 1f). p-Nitrophenol was tested because it has (>4 μL) was added to the solution, nanoparticles were
an acidic aromatic hydroxyl group like hydroquinone and precipitated at the interface between DMSO and hexane.
the nitro group is electron withdrawing like a manganese HBF4 can form primary ammonium salts with oleylamine
tricarbonyl moiety. Even when excess p-nitrophenol was and likely leads to NP solubility in DMSO by forming a
added to the solution, there was no transfer of Fe3O4 bilayer with the alkyl chains of oleic acid on the surface of the
nanoparticles from hexane to DMSO and no aggregation nanoparticles in DMSO. To test this, an oleylammonium salt
occurred. Formic acid (4 μL, pKa ≈ 3.75) was tested and was made by mixing oleylamine and HBF4 in hexane. The
found not to cause transfer of the Fe3O4 nanoparticles. resulting oleylammonium-BF4- salt is soluble in DMSO.
From those results, it can be assumed that acid plays an When the salt and nanoparticles were mixed and shaken in
important role in the transfer of nanoparticles from hexane hexane and DMSO, all nanoparticles were transferred from
to DMSO. Since pKa1= 3 for [(η6-hydroquinone)Mn(CO)3]- the hexane layer to the DMSO layer (Figure 1j). This result
BF4 in MeCN/water (Scheme 1), it can be guessed that acids supports the suggestion that a bilayer can be formed between
having a pKa below 3 should produce nanoparticle transfer oleylammonium-BF4- salts and surfactants (oleic acid)
to DMSO. From the pKa values of acids used in this on the nanoparticle when transfer to DMSO initiated by
5344 Organometallics, Vol. 28, No. 18, 2009 Kim et al.

[(η6-hydroquinone)Mn(CO)3]BF4 takes place. To support complexes, which are coordinated to platinum atoms on the
the formation of a bilayer, ammonium tetrafluoroborate surface of FePt nanoparticle (vide infra).
(NH4BF4) in DMSO and Fe3O4 nanoparticles in hexane [(η6-C6H5OH)Mn(CO)3]BF4 also showed the same trend
were combined and shaken for 2 h. There was no transfer of as [(η6-hydroquinone)Mn(CO)3]BF4. It can produce HBF4
Fe3O4 nanoparticles to the DMSO layer (Figure 1k), even through the equilibrium [(η6-C6H5OH)Mn(CO)3]BF4 T
after additional shaking overnight. It is concluded that there [(η5-C6H5O)Mn(CO)3] þ HBF4 in DMSO.18 [(η6-C6H5OH)-
cannot be transfer of Fe3O4 NPs from hexane to DMSO Mn(CO)3]BF4 in DMSO and FePt nanoparticles in hexane
without an ammonium salt having a long alkyl chain (bilayer were combined (Figure 2e) and shaken for 2 h. All FePt
formation). It was also found that tetrabutylammonium nanoparticles in the hexane layer transferred to the DMSO
tetrafluoroborate (TBABF4) does not lead to NP transfer layer (Figure 2f). Oleylamine was then added and the reac-
to DMSO, which is not surprising because TBABF4’s carbon tion mixture was shaken for 2 h. All FePt nanoparticles in the
chain length is short compared with oleylamine and oleic DMSO layer went back to the hexane layer (Figure 2g). [(η6-
acid (Figure 1l) and bilayer formation is not as facile. Dimethoxybenzene)Mn(CO)3]BF4 in DMSO and FePt na-
[(η6-Dimethoxybenzene)Rh(COD)]BF4 complex has no noparticles in hexane were combined and shaken for 2 h
acidic proton and cannot produce HBF4 in polar solvents (Figure 2h), and there was no transfer of NPs from hexane to
(e.g., DMSO and DMF). Nevertheless, [(η6-dimethoxyben- DMSO. [(η4-Quinone)Mn(CO)3]Li in DMSO does not in-
zene)Rh(COD)]BF4 in DMSO and Fe3O4 nanoparticles in duce NP transfer (Figure 2i), suggesting that the anionic
hexane upon shaking led to NP transfer to the DMSO. In the species [(η4-quinone)Mn(CO)3]- does not displace unproto-
case of [(η6-dimethoxybenzene)Mn(CO)3]BF4, there was no nated oleylamine from the surface of FePt nanoparticles.
transfer. [(η6-Dimethoxybenzene)Rh(COD)]BF4 is known To study the acid effect with FePt nanoparticles, formic
to be labile to ligand displacement (phosphine, amine, etc.) acid (pKa =3.75), phosphoric acid (pKa = 2.12), p-nitro-
so that oleylamine coordination to rhodium can occur, phenol (pKa ≈ 7.2), and HBF4 (pKa = -4.9) were selected.
resulting in transfer to DMSO. This ligand exchange by Formic acid (4 μL) (Figure 2j), phosphoric acid (4 μL)
oleylamine was confirmed by NMR of the free ligand (Figure 2k), and p-nitrophenol (20 mg) (Figure 2l) did not
(dimethoxybenzene) liberated from the complex (Figure S1). lead to NP transfer to DMSO. In the case of p-nitrophenol,
The oleylamine-coordinated rhodium complex likely forms a even after a large excess was added to the solution there
bilayer on the NP surface, and this leads to solubility in was no change. When an excess amount of phosphoric acid
DMSO. (>4 μL) or formic acid (>4 μL) was added, nanoparticles
In addition to Fe3O4, surface modification of FePt nanopar- were aggregated at the interface of DMSO and hexane or in
ticles was studied. FePt nanoparticles in hexane and DMSO. This means that although phosphoric acid (or
[(η6-hydroquinone)Mn(CO)3]BF4 in DMSO (Figure 2b) were formic acid) can react with surfactants, the product of the
combined and shaken for 2 h, and the FePt nanoparticles were reaction does not alter the surface sufficiently to allow
transferred to the DMSO layer (Figure 2c). With free hydro- solubility in DMSO. Only HBF4 led to FePt nanoparticle
quinone, there was no transfer of the nanoparticles from transfer to DMSO (Figure 2m).
hexane to DMSO (Figure 2a). When oleylamine is added to Because FePt nanoparticles have oleylamine as a surfac-
the surface-modified FePt nanoparticles in DMSO and shaken tant like the Fe3O4 nanoparticles, the formation of oleylam-
for 2 h, the FePt nanoparticles transferred back from the monium-BF4- salt (from HBF4) can be one of the factors
DMSO layer to the hexane layer (Figure 2d). It seems probable that cause FePt nanoparticles to be soluble in DMSO
that excess oleylamine replaced both the oleylammonium- (Figure 3). To confirm the effect of oleylamines on the
BF4--forming bilayer and the [(η5-semiquinone)Mn(CO)3]BF4 surface of FePt nanoparticle, the composition of FePt

Figure 2. (a) Hydroquinone in DMSO and FePt NPs in hexane were combined and shaken for 2 h, (b) [(η6-hydroquinone)Mn-
(CO)3]BF4 and FePt NPs in hexane before shaking, (c) after shaking (b) for 2 h, (d) addition of oleylamine to (c) and shaking it for 2 h,
(e) [(η5-phenol)Mn(CO)3]BF418 in DMSO and FePt NPs in hexane, (f) after shaking (e) for 2 h, (g) after shaking (f) with oleylamine, (h)
[(η6-dimethoxybenzene)Mn(CO)3]BF4 in DMSO and FePt NPs in hexane were shaken, (i) [(η4-quinone)Mn(CO)3]Li in DMSO and
FePt NPs in hexane were combined and shaken for 2 h, (j) formic acid in DMSO and FePt NPs in hexane were combined and shaken for
2 h, (k) phosphoric acid in DMSO and FePt NPs in hexane were combined and shaken for 2 h, (l) p-nitrophenol in DMSO and FePt NPs
were combine and shaken for 2 h, (m) HBF4 in DMSO and FePt NPs in hexane were combined and shaken for 2 h, (n) [(η6-
hydroquinone)Mn(CO)3]BF4 and Fe70Pt30 NPs in hexane were combined and shaken for 2 h.
Article Organometallics, Vol. 28, No. 18, 2009 5345

Figure 3. Proposed mechanism for the surface modification of FePt nanoparticle via [(η6-hydroquinone)Mn(CO)3]BF4: (a) surface
structure of as-made FePt nanoparticle, (b) surface structure of the surface-modified FePt nanoparticle, (c) TEM image (scale bar:
50 nm) and EDX spectrum (Figure S4a) of FePt nanoparticle before surface modification, (d) TEM image (scale bar: 50 nm) and EDX
spectrum (Figure S4c) of the surface-modified FePt nanoparticle.

nanoparticle was varied. Oleic acid molecules are coordi- The 587 cm-1 band is from Fe-O stretching. The FTIR
nated to Fe atoms of the surface of FePt nanoparticles, and spectrum of the [(η5-semiquinone)Mn(CO)3] complex coor-
oleylamines are coordinated to Pt atoms of the surface. dinated to Fe3O4 nanoparticles, shown in Figure 5b, was
Therefore, the amount of oleylamine on the surface of the collected after removing excess complex by adding a DMSO
nanoparticle can be controlled by the composition of the solution of the surface-modified Fe3O4 nanoparticles to
FePt nanoparticle. The Fe70Pt30 nanoparticle was synthe- THF and collecting the resulting precipitates with a magnet.
sized and its composition was confirmed by EDX. This The collected Fe3O4 nanoparticles were washed with fresh
Fe70Pt30 nanoparticle has fewer Pt atoms on the surface in THF and dried under vacuum. The peaks at 2047 and 1977
comparison with the generic Fe52Pt48 nanoparticle, whose cm-1 have been assigned to the carbonyl stretches of [(η5-
composition is almost half Fe and half Pt. [(η6-Hydroqui- semiquinone)Mn(CO)3] binding to the surface of the nano-
none)Mn(CO)3]BF4 in DMSO and Fe70Pt30 nanoparticles in particle. The peak at 1632 cm-1 is due to the oleic acid
hexane were combined and shaken for 2 h. There was no binding to the surface of the nanoparticle. The peaks at 2921
transfer of Fe70Pt30 nanoparticles from the hexane layer and 2851 cm-1 are due to the C-H stretching modes of
(Figure 4a). From this experiment, it can be surmised that surfactants. The peaks at 1030 and 950 cm-1 have been
the amount of oleylamine that is coordinated to Pt atoms of assigned to Fe3O4 surface-bound DMSO molecules.
the surface of FePt nanoparticles is related to the solubility in The FTIR spectrum of [(η5-semiquinone)Mn(CO)3] itself
DMSO after treatment with [(η6-hydroquinone)Mn(CO)3]- (Figure 5e) shows peaks at 2066 and 1967 cm-1 due to the
BF4 (Figure 4b). tricarbonyl stretches. By comparing Figure 5b with
The FTIR spectrum of Fe3O4 nanoparticles, shown in Figure 5e, it can be seen that the peaks (2047 and 1977 cm-1)
Figure 5a, was collected after removal of the excess surfac- due to the carbonyl stretching of [(η5-semiquinone)Mn-
tants by washing two times. One washing cycle involved (CO)3] on the nanoparticle have been shifted from the
precipitating the particles with ethanol and redispersing complex itself (2066 to 2047 cm-1). This can be taken as
them in hexane. Oleic acid molecules show strong CH2 bands good evidence for the complex binding to the nanoparticles.
at 2920 (νa C-H), 2852 (νs C-H), and 1405 (ν C-H).19,20 The FTIR spectrum of Fe3O4 nanoparticles treated with
HBF4 is shown in Figure 5d and indicates the presence of the
(18) Lee, S.-G.; Kim, J.-A.; Chung, Y. K.; Yoon, T.-S.; Kim, N.-J.; carboxylate group from oleic acid (asymmetric mode at 1632
Shin, W.; Kim, J.; Kim, K. Organometallics 1995, 14, 1023–1029. cm-1). The peaks at 1030 and 950 cm-1 seem to be due to
(19) Lan, Q.; Liu, C.; Yang, F.; Liu, S.; Xu, J.; Sun, D. J. Colloid DMSOs bound to the nanoparticles. The peak at 586 cm-1
Interface Sci. 2007, 310, 260–269.
(20) Klokkenburg, M.; Hilhorst, J.; Erne, B. H. Vib. Spectrosc. 2007, can be due to the vibrations of the crystalline lattice of
43, 243–248. nanocrystalline magnetite.20 The FTIR spectrum of the
5346 Organometallics, Vol. 28, No. 18, 2009 Kim et al.

Figure 4. Proposed surface structure “before” and “after” the surface modification of FeXPt100-X nanoparticle: (a) Fe70Pt30
nanoparticle; EDX spectrum (Figure S4b) and (b) Fe52Pt48 nanoparticle; EDX spectrum (Figure S4c).

Figure 5. FTIR spectra (in KBr) of (a) as-made Fe3O4 NPs, (b) Figure 6. FTIR spectra (in KBr) of (a) as-made FePt NPs, (b)
the surface-modified Fe3O4 NPs having [(η5-semiquinone)Mn- [(η5-semiquinone)Mn(CO)3] ligand-exchange FePt NPs, (c)
(CO)3] complexes, (c) the surface-modified Fe3O4 NPs having after HBF4 in DMSO and FePt NPs in hexane were combined
[(η4-quinone)Mn(CO)3]Na (after treatment of (b) with NaOAc), and shaken for 2 h, and (d) free [(η5-semiquinone)Mn(CO)3]
(d) after HBF4 in DMSO and Fe3O4 NPs in hexane were complex.
combined and shaken for 2 h, and (e) [(η5-semiquinone)Mn-
(CO)3] complex, (f) [(η4-quinone)Mn(CO)3]Na complex. of [(η4-quinone)Mn(CO)3]- bound to the nanoparticles
(2027, 1953 cm-1, Figure 5c) are higher than that of free
[(η4-quinone)Mn(CO)3]- ligand-exchanged Fe3O4 nanopar- [(η4-quinone)Mn(CO)3]- (2015, 1935, 1899 cm-1, Figure 5f)
ticles, shown in Figure 5c, was collected after adding indicates electronic communication between the nanoparti-
NaOAc 3 3H2O to the DMSO solution of [(η5-semiquinone)- cle and the bound complex.
Mn(CO)3]-bound Fe3O4. Removal of excess NaOAc 3 3H2O The FTIR spectrum of the as-made FePt nanoparticles
and excess [(η4-quinone)Mn(CO)3]- was accomplished by shown in Figure 6a was collected after removing the excess
magnetic separation. The peaks at 2027 and 1953 cm-1 have surfactants by washing the particles three times. One wash-
been assigned to the tricarbonyl vibrations of [(η4-quinone)- ing cycle involved precipitating the particles with ethanol
Mn(CO)3]- bound to the nanoparticles. The peaks at 2047 and redispersing in hexane. The peaks at 2921 and 2852 cm-1
and 1977 cm-1 in Figure 5b were shifted to the lower values are from C-H asymmetric stretching and C-H symmetric
of 2027 and 1953 cm-1 in Figure 5c. This means that [(η5- stretching of the -CH2- groups in both oleylamine and
semiquinone)Mn(CO)3] complexes on the nanoparticle were oleic acid. The peaks at 2041 and 1966 cm-1 are from the
deprotonated by NaOAc 3 3H2O, resulting in increased tricarbonyls of [(η5-semiquinone)Mn(CO)3] binding to the
π-back-bonding. The reason that the tricarbonyl vibrations FePt nanoparticles (Figure 6b).
Article Organometallics, Vol. 28, No. 18, 2009 5347

Table 1. Atomic Ratios (determined by EDX) of the Surface-

Modified Fe3O4 NPs
Fe (%)d S (%)d Mn (%)d
Fe3O4 NP-SQMTC a 93.62 5.30 1.09
Fe3O4 NP-BF4b 93.75 6.25 0
Fe3O4 NP-QMTC c 88.33 2.11 9.56
a
Fe3O4 NPs in hexane and [(η6-hydroquinone)Mn(CO)3]BF4 in
DMSO were combined and shaken for 2 h (Figures 1c, 3d), b Fe3O4
NPs in hexane and HBF4 in DMSO were combined and shaken for 2 h
(Figures 1f, 3c), c To a DMSO solution of the surface-modified Fe3O4
NPs and excess noncoordinated [(η5-semiquinone)Mn(CO)3]
(Figure 1c) was added NaOAc 3 3H2O (Figure 8b). d Atomic ratio
determined by EDX.

coordinated to the Fe metal atoms on the surface of Fe3O4

nanoparticles and not by simple physical adsorption.
Figure 8 shows the proposed mechanism for the ligand
exchange of nanoparticles.
From both Figure 7c and Figure 7d, it can be seen that
HBF4 can detach oleylamines on the nanoparticle’s surface
by forming oleylammonium-BF4- salts and that oleylam-
monium-BF4- salts can form a bilayer with oleic acid, which
is coordinated on the nanoparticle’s surface. The nanopar-
ticles that are transferred from the hexane layer to the
DMSO layer via HBF4 or [(η6-hydroquinone)Mn(CO)3]BF4
have vacant sites where oleylamines left and both [(η5-
semiquinone)Mn(CO)3] and DMSO (solvent) subsequently
coordinate (Figure 7a). Figure 8b shows not only that [(η5-
Figure 7. Surface modification of (a) a nanoparticle having semiquinone)Mn(CO)3] complexes on the surface of the
oleylamine and oleic acid via (b) [(η6-hydroquinone)Mn(CO)3]- Fe3O4 nanoparticle can be switched to [(η4-quinone)Mn-
BF4, (c) HBF4, and (d) oleylamonium-BF4. (CO)3]- but also that free [(η4-quinone)Mn(CO)3]- can re-
place DMSOs that are coordinated to Fe atoms at the
From comparing the carbonyl stretching frequency (2041 surface.
and 1966 cm-1) of the [(η5-semiquinone)Mn(CO)3] complex Both FTIR spectra and EDX data support Figure 7b. In
binding to the FePt nanoparticle with the tricarbonyl stretch- the EDX data of [(η4-quinone)Mn(CO)3]- bound to Fe3O4
ing frequency (2047 and 1977 cm-1) for binding to the Fe3O4 nanoparticles, the atomic ratio of Mn was 9.56% and the
nanoparticle, it can be seen that there are differences between atomic ratio of sulfur from DMSO was 2.11% (Table 1 and
the two nanoparticle systems. The complexes are interacting Figure S3c). However, EDX data of [(η5-semiquinone)Mn-
with different metals on the surface: with Fe atoms in the case (CO)3]-bound Fe3O4 nanoparticles showed the that the
of Fe3O4 and with Pt in the case of FePt. atomic ratio of Mn (1.09%) was lower than that of sulfur
From the FTIR spectra, EDX, and other control experi- (5.30%) from DMSO (Table 1 and Figure S3a). The reversal
ments with the Fe3O4 nanoparticles and the FePt nanopar- of atomic ratio between Mn and S in the EDX after the
ticles, the plausible surface structures in DMSO are as deprotonation process (Figure 8) seems to be from the
indicated in Figure 7. Figure 7a shows a nanoparticle with replacement of DMSOs coordinated to Fe atoms by
both oleylamine and oleic acid on the surface. Figure 7b [(η4-quinone)Mn(CO)3]- complexes due to the higher
shows that the nanoparticle has a bilayer structure in DMSO coordination strength of [(η4-quinone)Mn(CO)3]- com-
when [(η6-hydroquinone)Mn(CO)3]BF4 is added to a bipha- plexes (anionic complex) compared to DMSO (neutral polar
sic solution (hexane/DMSO). Figure 7c shows the nanopar- molecule).
ticle in DMSO solution when HBF4 acid is added to the In summary, selective displacement of oleylamines from
biphasic solution (hexane/DMSO). Figure 7d shows the the nanoparticles (Fe3O4 and FePt) having both oleylamines
nanoparticle with just a bilayer between the surfactant and and oleic acids as surfactants via treatment with [(η6-
oleylammonium-BF4- salts on the surface. hydroquinone)Mn(CO)3][BF4] renders the nanoparticles so-
In case of the surface-modified Fe3O4 nanoparticle having luble in DMSO (polar solvent). The acid HBF4 (generated
[(η5-semiquinone)Mn(CO)3] complexes on the surface from the dissociation of [η6-hydroquinone)Mn(CO)3]BF4 in
(Figure 7b), EDX data showed sulfur from DMSO and DMSO) promotes selective decoordination of oleylamines
Mn from [(η5-semiquinone)Mn(CO)3] on the surface of the from the nanoparticles and subsequent coordination of a
nanoparticle with the atomic ratio of the sum of Mn (1.09%) ligand such as [(η5-semiquinone)Mn(CO)3] or DMSO. This
and sulfur (5.30%) ca. 6-7% (Table 1 and Figure S3a). In is a facile route to the displacement of oleylamines without
the case of the surface-modified Fe3O4 nanoparticle via using stronger field ligands than oleylamine itself. It was
HBF4 (Figures 1f, 7c), EDX showed that the atomic ratio observed that tricarbonyl stretches are varied according to
of sulfur from DMSO was ca. 6-7% (Table 1 and the nanoparticle metal when [(η5-semiquinone)Mn(CO)3]
Figure S3b). These two EDX data imply that the space for coordinates. Thus, when [(η5-semiquinone)Mn(CO)3] coor-
ligand exchange by the [(η5-semiquinone)Mn(CO)3] com- dinates to Fe on the surface of an Fe3O4 nanoparticle, it has
plexes or DMSO is limited and indicates indirectly that higher tricarbonyl stretching frequencies than it does when
[(η5-semiquinone)Mn(CO)3] complexes and DMSO are coordinated to Pt on the surface of a FePt nanoparticle.
5348 Organometallics, Vol. 28, No. 18, 2009 Kim et al.

Figure 8. Proposed mechanism of (a) the surface modification of Fe3O4 nanoparticle due to [(η6-hydroquinone)Mn(CO)3]BF4 and
(b) switching [(η5-semiquinone)Mn(CO)3] complexes to [(η4-quinone)Mn(CO)3]- complexes on the surface-modified Fe3O4 nano-
particle using the base NaOAc.

When [(η4-quinone)Mn(CO)3]- coordinates to Fe3O4 nano- polar aprotic organic solvent such as DMSO and DMF may
particles, its tricarbonyl stretching frequency is higher com- have applications in catalysis, gas storage, and electronic
pared with the free [(η4-quinone)Mn(CO)3]-Naþ complex, materials.
showing that the nanoparticle functions as an electron
reservoir.21 Acknowledgment. We are grateful to the donors of
It is expected that the formation of the surface-modified the Petroleum Research Fund, administered by the
nanoparticles soluble in DMSO (polar aprotic organic American Chemical Society, to the National Science
solvent) will provide more options for surface modification Foundation (CHE-0308640), to the Corinna Borden
of nanoparticles having oleylamines and oleic acids as sur- Keen Research Fellowship, and to the Dean Peder Estrup
factant. Present work in our group is being focused on Graduate Student Research Fellowship for support of
formation of metal-organometallic or metal-organic coordi- this research.
nation polymers on metallic or metal oxide nanoparticles
having both oleylamines and oleic acids. Processability in Supporting Information Available: Experimental details and
1
H NMR, PXRD, and EDX spectra. This material is available
(21) Cao, D.; He, P.; Hu, N. Analyst 2003, 128, 1268–1274. free of charge via the Internet at http://pubs.acs.org.