Synthesis of photoswitchable magnetic Au-Fullerosome hybrid nanomaterials for permittivity enhancement applications

Article abstract of DOI:10.3390/molecules200814746

We designed and synthesized several nanomaterials 3 of three-layered core-shell (γ-FeOxAuNP)[C60(>DPAF-C9)1or2]n nanoparticles (NPs). These NPs having e-polarizable fullerosome structures located at the outer layer were fabricated from highly magnetic cor

Full text of DOI:10.3390/molecules200814746

Molecules 2015, 20, 14746-14760; doi:10.3390/molecules200814746
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molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Synthesis of Photoswitchable Magnetic Au–Fullerosome Hybrid
Nanomaterials for Permittivity Enhancement Applications
Min Wang 1, Seaho Jeon 1, Chefu Su 2, Tzuyang Yu 2, Loon-Seng Tan 3 and Long Y. Chiang 1,*
1
Department of Chemistry, Institute of Nanoscience and Engineering Technology,
University of Massachusetts Lowell, Lowell, MA 01854, USA;
E-Mails: wangmin81@gmail.com (M.W.); seaho_jeon@uml.edu (S.J.)
2
Department of Civil and Environmental Engineering, University of Massachusetts Lowell, Lowell,
MA 01854, USA; E-Mails: CheFu_Su@student.uml.edu (C.S.); TzuYang_Yu@uml.edu (T.Y.)
3
Functional Materials Division, AFRL/RXA, Air Force Research Laboratory,
Wright-Patterson Air Force Base, Dayton, OH 45433, USA;
E-Mail: Loon-Seng.Tan@wpafb.af.mil
* Authors to whom correspondence should be addressed; E-Mail: Long_Chiang@uml.edu;
Tel.: +1-978-934-3663; Fax: +1-978-934-3013.
Academic Editor: Derek J. McPhee
Received: 9 July 2015 / Accepted: 7 August 2015 / Published: 13 August 2015
Abstract: We designed and synthesized several nanomaterials 3 of three-layered core-shell
(γ-FeOx@AuNP)@[C60(>DPAF-C9)1or2]n nanoparticles (NPs). These NPs having e−-polarizable
fullerosome structures located at the outer layer were fabricated from highly magnetic
core-shell γ-FeOx@AuNPs. Fullerosomic polarization of 3 was found to be capable of causing
a large amplification of material permittivity that is also associated with the photoswitching
effect in the frequency range of 0.5‒4.0 GHz. Multilayered synthetic construction allows
Förster resonance energy transfer (FRET) of photoinduced accumulative surface plasmon
resonance (SPR) energy in the gold layer to the partially bilayered C60(>DPAF-C9)1or2-derived
fullerosome membrane shell layer in a near-field of direct contact without producing radiation
heat, which is commonly associated with SPR.
Keywords: fullerenyl chromophore conjugates; gold-fullerosome hybrid nanomaterials;
core-shell nanoparticles; permittivity; relative dielectric constant enhancement

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1. Introduction
Recent development of surface plasmon resonance (SPR) energy phenomena has been demonstrated
and applied in many technological areas including the use of it as an alternative means to increase either
light absorption or scattering in a thin film to enhance solar cells efficiency [1,2]. In general, SPR energy
arises in silver or gold nanoparticles (NPs) as collective oscillation of surface electrons that is induced
by the interaction with the electric field of the incident light. Light absorption is achievable when the
size of NPs is controlled to be smaller than the wavelength of the incident light. It leads to polarization
with the formation of polaritons. The degree of polarizability leading to the influence of absorption
cross-section enhancement larger than the actual physical cross-section of the NPs can be a function of
particle size and shape, refractive index, direction of electric field, and characteristics of surrounding
medium [3]. For example, light absorption is proposed to be the dominate event over scattering if the
particle size is smaller than ~15 nm. Gold NPs are very inefficient light emitters. Therefore, most of
absorbed photoenergy is converted into irradiation heat to surrounding medium. However, if a single or
arrays of gold NPs or nanometer-scaled dipole wires [4] can be fabricated, they may behave as antennas
working at optical frequency [5–8] due to their strong interactions with the incident light. This is different
from traditional microwave frequency antenna that is a mediator between far-field radiation and local
fields (currents) in an electronic circuit.
The simplest and convenient synthetic methods for the preparation of gold nanostructures include wet
chemical synthesis [9–11] and the sol process [12]. By synthetically creating the shape preference to
increase the aspect ratio (length/width ratio) leading to anisotropic gold nanorods, their plasmon mode may
become tunable upon splitting into two visible bands. This provides the possibility to tune the resonance
energy band to match with dielectric materials for permittivity modulation. In addition, crystallographic
facets if synthetically achievable may also exhibit different thermodynamic or photocatalytic properties
from those of spherical nanoparticles. These are indicative of parameters to potentially impact materials
characteristics and photoresponse ability by modification of gold nanostructures when applied in
conjunction with dielectrics.
Refractive index of a given medium is a function of the product of dielectric constant or permittivity
(ε) and permeability (µ). Both are relevant material parameters in response to electromagnetic waves.
The former parameter is dependent on material’s degree of polarization at the wavelength of measurements.
Accordingly, we designed and synthesized several electron-polarizable donor-acceptor conjugates using
C60 cage as the acceptor moiety and highly photoresponsive, light harvesting DPAF-Cn chromophore as
the donor antenna to construct the corresponding conjugates C60-(antenna)x [13,14]. We also applied
additional photoinduced SPR energy for the aim to cause further molecular e‒-polarization of such
conjugates. This type of polarization arises from the induced intramolecular electron-transfer process going
from the donor antenna to the e‒-accepting fullerene cage in an ultrafast kinetic rate in femtoseconds [15].
To achieve the near-field effect during the energy-transfer event between plasmonic Au NPs and
C60-(antenna)x, we assembled a multiple layered structure of nanoparticles having an inner magnetic
γ-FeOx@AuNP core encapsulated by an outer C60(>DPAF-C9)x shell that is coupled with control of the
thickness among each layer. Apparently, fabricated core-shell structural configurations are capable of
inducing permittivity amplification at RF-frequency ranges.

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2. Results and Discussion
The C60 cage is highly electronegative, a feature associated with its strongly electron-accepting ability.
In the presence of a covalently bound electron-donating chromophore, such as 9,9-di(3,5,5-trimethylhexyl)-
2-diphenylaminofluorene (DPAF-C9), high molecular e‒-polarizability characteristics can be achieved
in the conjugate upon photoexcitation [16]. The phenomena arise from intramolecular charge-transfer
event among e‒-donating DPAF-C9 moieties and the e‒-accepting C60, leading to the formation of a
negatively charged (C60>)−· cage and positively charged (DPAF)+·-C9. In our recent studies of femtosecond
transient absorption measurements, we have synthesized and presented an approach of C60/or
C70-(antenna)x type fullerene-chromophore dyads [14,15], triads, and pentaads [17,18] using similar C60/or
C70(A)–keto–DPAF-C9(D) assembly structures. This A‒D design as that of C60(>DPAF-C2) (Figure 1) takes
the advantage of both C60> and DPAF-C9 being active in linear and nonlinear photonic processes [14].
Its photoresponsive activity was verified by intramolecular energy/or electron-transfer processes and
found to occur in an ultrafast rate of <130 fs [15]. In PhCN, electron-transfer process was found to
−
dominate photophysical events giving the charge-separated state C60 ·(>DPAF+·-Cn)1or2 in a long
life-time [17]. A closely linked molecular nanostructure with periconjugation between C60 and the carbonyl
moiety of DPAF-Cn in a spacing distance of only ~3.5 Å [15], as shown in Figure 1a, and the concurrence
of keto-enol tautomerism at the conjugation bridge in Figure 1b were reasoned for the observed ultrafast
photoresponsive rate. The latter leads to the creation of partial conjugation between C60 and covalently
linked DPAF-Cn separated by only one carbon atom (C61). This makes the photoinduced intramolecular
electron-transfer very efficient and ultrafast.
(a)
(b)
(c)
~3.5 Å
(δ: 5.69)
(C60 cage)
C60(>DPAF-C2)
Figure 1. Bridging structure of a C60-DPAF-C2 conjugate with (a) carbon-carbon bond
lengths at the C60 cage (CF1 and CF2) bridging unit indicated showing a shorter length of
C61‒C(=O) than a normal single C‒C bond, as determined by X-ray single crystal structural
analysis reported previously [15]; (b,c) Keto-enol tautomerism of the bridging unit structure
showing a large downfielded chemical shift of α-proton Hα from the normal α-proton chemical
shift of δ 2.1‒2.3. This downfield shift is also caused partly by the fullerenyl ring current.
Synthesis of electronically polarizable push-pull conjugative structures as methano[60]fullerene dyad
C60(>DPAF-C9) 1 and triads C60(>DPAF-C9)2 2 was performed by using modified synthetic procedures
reported recently [15], as outlined in Scheme 1 with the reagent and conditions indicated. The key precursor
intermediate BrDPAF-C9 6 was synthesized from 9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene (5)

Molecules 2015, 20
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with α-bromoacetyl bromide in the presence of Lewis acid for a period of 4.0 h. Subsequent fullerene
condensation reaction was carried out by the treatment of 6 with C60 using DBU as a base to yield both
1 and 2 in a yield of 70 and 14%, respectively, after chromatographic purification on SiO2.
N
ii
i
Br
N
Br
4
3
5
O
iii
O
O
O
iv
iv
N
N
Br
6
, BrDPAF-C9
1, C60(>DPAF-C9)
N
2
, C60(>DPAF-C9)2
Scheme 1. Synthesis of C60-(antenna)x nanostructures 1 (x = 1) and 2 (x = 2) [14]. Reagents
and reaction conditions: (i) 1-C9H37-OMs, t-BuOK in THF, 0 °C‒r.t., 4 h; (ii) diphenylamine,
tris(dibenzylideneacetone)dipalladium(0) (cat.), rac-BINAP (cat.), t-BuONa, toluene, 110 °C,
8.0 h; (iii) α-bromoacetyl bromide, AlCl3, ClCH2CH2Cl, 0 °C, 4.0 h; (iv) C60, DBU, toluene,
r.t., 5.0 h.
Spectroscopic characterization of monoadduct 1 and bisadduct 2 was made by their positive ion fast
atom bombardment mass spectrum (FAB+‒MS) showing clearly the molecular ion mass at m/z 1345/1346
(M+/MH+) and 1971 (M+) for 1 and 2, respectively. Both spectrum displayed a fragmentation peak at
m/z 720/721 corresponding to the ion mass of C60 cage with no major detectable intermediate fragments
indicating the main bond breakage occurring at the cyclopropanyl carbon conjunction to C60 cage.
We assigned all major proton peaks in 1H-NMR spectrum of 1 and 2. Since the compound 1 is a single
component, its spectrum can be used as a reference to assist chemical shift assignments of 2. The α-proton
(Ha next to the carbonyl group) peak of 1 appeared as a triplet (via through space coupling with two
fluorenyl protons in vicinity) at δ 5.69 (Figure 2a) with a large downfield shift of roughly 1.2 ppm from that
of 6. It was also accompanied with downfield shift of all fluorenyl phenyl protons to 7.83 (d, J = 8 Hz), 8.48
(d, J = 8 Hz), and 8.34 (s). In Figure 2b, we assigned the multiplet peaks at δ 7.7‒7.9 (2H), 8.2‒8.35
(2H), and 8.35‒8.6 (2H) to the chemical shift of three types of fluorenyl protons. There are two groups
of proton peaks at δ 5.35‒5.6 and 5.6‒5.85 in a different integration intensity accounted for a total of two
types of α-protons each with Ha and Hb in a slightly different chemical shift value. These revealed only two
regioisomers possible for the bisadduct 2 in a molecular ratio of roughly 1:2.8 in a chromatographically
non-separable fraction due to close similarity of the molecular polarity between these two regioisomers.
Highly steric hindrance of DPAF-C9 antenna was reasoned for the isolation of a very limit number
of regioisomers.

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Figure 2. 1H-NMR spectra of (a) the monoadduct C60(>DPAF-C9) 1 and (b) the bisadduct
C60(>DPAF-C9)2 2. Chemical shift of the Ha proton of 1 was used to assign Ha and Hb
protons of 2 that revealed only one major and one minor regioisomer existing in the
chromatographically purified sample; (c) 13C-NMR spectrum of 1 indicating a C2 molecular
symmetry with a total of 29 fullerenyl sp2 carbons.
Preparation of 1 or 2-encapsulated γ-FeOx@AuNP trilayered core-shell nanoparticles, (γ-FeOx@AuNP)
@[C60(>DPAF-C9)x]n 3–1 (x = 1) or 3–2 (x = 2) was made first by the synthesis of magnetic γ-FeOx
nanoparticles using either the method A1 or A2 described in the experimental section. The latter method
carried out at 320 °C gave monodisperse nanocrystals. The former method performed at 150 °C resulted
in smaller NPs, as shown in Figure 3a. Two methods B1 and B2, as described in the experimental section,
were applied for deposition of the gold layer. The latter method involves dissolution of iron oxide NPs
by (CH3)4N+OH‒ in H2O, followed by the attachment of sodium citrate upon stirring for the reduction of
hydrogen tetrachloroaurate(III) trihydrate (HAuCl4·3H2O) along with hydroxylamine hydrochloride.
Since a magnetic core NP was used as the substrate for providing a magnetic field to interact with
electromagnetic waves, all coated core-shell γ-FeOx@AuNPs can be removed from solution easily by
an external magnet and purified. Surface of the resulting gold layer was stabilized by the addition of
1-octanethiol in toluene to furnish the products of core-shell Au-nanoparticles-coated γ-FeOx NPs.
Sufficient binding of 1-octanethiol as a capping agent rendered moderate solubility of NPs in organic
solvents ready for encapsulation by 1 and 2 under ultrasonication. The resulting relatively pure trilayered
core-shell nanoparticles can be retrieved easily from the washing solution (ethanol and ether) by an external
permanent magnet. The procedure provided separation of core-shell nanoparticles from the residual
capping agent and an excessive amount of C60(>DPAF-C9) in solution. The binding force of 1 and 2 to the
nanoparticle surface was controlled by the strong hydrophobic‒hydrophobic interaction forces of C60‒C60
cages that resulted in molecular self-assembly of C60(>DPAF-C9) to form a partial bilayer or bilayer

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configuration at the surface, resembling that found on the formation of bilayered fullerosome nanovesicles
of water-soluble C60(>DPAF-EGx) reported recently [19]. Accordingly, initial interactions of 1 at the
nanoparticle surface was designated to occur on two 3,5,5-trimethylhexyl moieties owing to low solubility
of C60> in alkanes that should push fullerene cages outward at the solvent interfacial area. The sonication
treatment provides sonochemical energy to invert 1 with the favor of C60 cage in contact with Au NPs
that gives the monolayer capping of the surface by C60(>DPAF-C9) molecules [20]. They become
accessible for the binding of the second layer of 1 in the solution based on strong C60‒C60 cage and
C60‒DPAF aromatic-ring attraction forces. This is proposed to be the formation mechanism of a partial
bilayered or bilayered fullerosome membrane covering γ-FeOx@AuNP nanoparticles as the nanostructure
configuration of (γ-FeOx@AuNP)@[C60(>DPAF-C9)x]n 3.
Figure 3. TEM micrographs of (a) γ-FeOx (prepared by the method A1); (b) γ-FeOx@AuNP,
and (c) C60(>DPAF-C9)-encapsulated γ-FeOx@AuNP nanoparticles 3–1 showing evolution
of particle morphology changes.
Morphology and topography of all NPs was investigated by tunneling electron microscopic (TEM)
micrographs. As a result, the average size of the parent γ-FeOx nanoparticles was measured to be small
as 5–10 nm in diameter (Figure 3a) in a narrow distribution. Upon deposition of a gold layer, only a
slight layer contrast difference between Au and FeOx was observed in Figure 3b that is still possible to
differentiate a darker core iron oxide particle diameter of ~9 nm with a slightly lighter gold shell thickness
of ~3.0 nm (inset of Figure 3b). Further coating of 1 at the outer shell led to encapsulation of many
nanoparticles by a layer of organic substance in light soft amorphous image (Figure 3c) that was measured
in a shell thickness of few nm. This thickness corresponds well to a proposed partial bilayered or bilayered
packing configuration of molecules 1 on the surface of γ-FeOx@AuNP. It is plausible to assume the
strong attraction force between the C60> cage and AuNP in directing the initial orientation of molecules

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1 having the fullerene cage directly associated with interfacial binding on Au surface that resulted in the
dialkylfluorene ring moiety facing outward to the solution media. Subsequent packing of more molecules
of 1 on the layer of DPAF-C9 is expectable to form a layer of fullerosome membrane owing to the stronger
hydrophobic–hydrophobic interaction forces of (C60>)–(C60>) than (C60>)–(DPAF-C9). By using the MM2
energy minimization technique to simulate the 3D molecular configuration with the assumption of a C60
cage diameter width of 1.0 nm, we estimated the molecular long-axis length of 1 in roughly 3.5 nm. This
fits well with the sum of an observed bilayer packing thickness of few nm, consisting of a head-to-head
orientation of 1 in the fullerosome membrane region.
Successful construction of core-shell nanomaterials was verified by their infrared spectra of purified
samples. Oleic acid sodium salt stabilized γ-FeOx NPs (Figure 4b) displayed three medium to weak bands at
1618 (s), 1459 (w), and 1407 (m) cm‒1 along with the main Fe-O absorption band centered at 578 (vs) cm‒1.
Incorporation of an Au layer on top does not change much on the main peak of spectrum in Figure 4c.
Deposition of the fullerosome layer of 1 on the outer layer obviously incurred major absorption band
changes in Figure 4d to show carbonyl (C=O) bands at 1741 (m), 1675 (m), and 1637 (m) cm‒1 that
revealed various bonding interactions of at least two moieties, one from oleic acid and the other carbonyl
group in solid state of 1. Olefin (C=C) absorption band of 1 centered at 1591 cm‒1 can be detected very
clearly. The most indicative strong sharp band at 526 cm‒1 of Figure 4d can be assigned to the half-cage
absorption of C60> that is consistent with that of 1 in Figure 4a.
(a) C60(>DPAF-C9)
C60>
(b) γ-FeOx w/ oleic acid salt
(c) γ-FeOx@AuNp w/ n-C8H17SH
(d) (γ-FeOx@AuNp)@[C60(>DPAF-C9)]
C60>
3000
2500
2000
1500
1000
500
Wavenumber (cm‒1)
Figure 4. Infrared absorption spectra of four samples indicated, showing a consecutive sum
of absorption bands on final product 3–1 in (d).
Optical absorption of the Au nanoparticle subshell layer is crucial for this study to allow us executing
and introducing photoinduced surface plasmon resonance energy generation at UV to visible light
wavelengths (300‒550 nm), followed by subsequent near-field SPR energy-transfer from the inner layer
to the outer C60(>DPAF-C9)x-derived fullerosome layer. This is in addition to the ability of 1 or 2 to
perform photoinduced intramolecular charge-separation themselves to the corresponding transient

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−
−
C60 ·(>DPAF+·-C9) state for 1 and C60 ·(>DPAF+·-C9)(>DPAF-C9) or C60−2(>DPAF+·-C9)2 states for 2 at
the same wavelength range covering roughly 250‒380 nm and 350‒430 nm corresponding to absorptions
of C60> and DPAF-C9 moieties, respectively. These absorption bands remain unchanged during the
fabrication procedure of 3–1, as shown in comparison between Figure 5c,d). The broad absorption band
(Figure 5b) of the Au layer covers the most of the spectrum wavelength range at 280–630 nm with the
extinction coefficient higher than that of γ-FeOx (Figure 5a).
Figure 5. UV-vis absorption of (a) γ-FeOx NPs stabilized by n-C10H21NH2; (b) γ-FeOx@AuNP
stabilized by n-C8H17SH; (c) C60(>DPAF-C9) 1 in CHCl3; and (d) 3–1 in CHCl3‒THF (1:5)
with their absorption correlation to emission bands (light blue) of white LED light used.
Frequency-dependent dielectric and permittivity measurements of 3–1 and 3–2 were carried out using
an open-ended coaxial probe and a network analyzer in the range of 0.5‒4.5 GHz to study properties
including the relative dielectric constant (εr′, the real part of complex permittivity) and the relative dielectric
loss factor (εr′′, the imaginary part of complex permittivity). It was conducted inside a custom-built
chamber to create a circumferentially uniform illumination environment. Inner chamber temperature was
maintained and controlled using several fans. Illumination periods were chosen to be 10, 30, and 60 min.
The objective of these measurements was to investigate the dielectric amplification of nanoparticles in
various core-shell layered configurations in response to external photoinduced generation of SPR effects
within the gold-shell layer. We selected a LED white light with the output power of 2.0 W and a
UVB-enhanced visible lamp with the output power density of 20 mW/cm2 for the study. With the use of
a white light, the optical absorption should occur mainly on the gold layer since the absorption peak
maximum (λmax) of C60> cage and DPAF-C9 moieties are centered at 326 and 410 nm, respectively.
Figure 6 shows relative dielectric constant (εr′) curves of 3–1, as an example, with the data taken at the
frequency of 1.0‒4.0 GHz during and after 60 min illumination. The inner chamber temperature was
monitored constantly during the irradiation period at the sample tube wall. In all experiments, white light
illumination led to a slight rise in temperature to 39‒52 °C in the first 10 min. Increase of chamber
temperatures from 25 °C resulted in corresponding small increases of the εr′ value of samples in a different
extent, as shown in Figure 6. The value remains relatively constant during further irradiation from 10 to

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60 min. In separate similar experiments using three reference samples of 1 alone, γ-FeOx NPs, and core-shell
γ-FeOx@[C60(>DPAF-C9)]n NPs without the Au layer, no detectable large change of εr′ values was
observed during or after the irradiation period. Therefore, observed large εr′ changes with the core-shell
sample 3–1 can be correlated to the εr′ value increase of C60(>DPAF-C9)-derived fullerosome membrane,
as a result of photoinduced plasmon-energy generation in the gold layer.
The sharp increase of permittivity can be accounted by a ratio of εmax′/εo′ (εo′ = 2.25 at 1.0 GHz and
time zero) in a roughly 2.89-fold or 1.91-fold (εmax′/εr′, based on εr′ = 3.4 at 60 min) at the epak maximum
reached at roughly at the time of 70 min (10 min after the start of light-off state). This is considered to
be a novel switch-on permittivity phenomenon that we have observed to date. We hypothesized that the
release of SPR energy from the intermediate gold layer sandwiched between the layers of fullerosome
membrane and core γ-FeOx Np caused activation of the molecular polarization of C60(>DPAF-C9)x
molecules to its transient charge-separate (CS) state. This CS state consists of a positively charged
electron-donor moiety (DPAF)+·-C9 and a negatively charged electron-acceptor moiety (C60>)‒·. This is
in a large contrast to no clear change of εr′ values of core-shell nanoparticles without incorporation of an
Au-layer at the light switch-off stage. Subsequently, the amplified εr′ underwent a relaxation process
back to the initial values within the next 20 min, revealing good recyclability and photoswitchability
during light-on and light-off cycles.
(accumulated light dosage: ~12.8 J/cm-2)
50
45
40
35
30
25
20
7
6
5
4
3
2
1.0 GHz
2.0 GHz
3.0 GHz
4.0 GHz
Light-on
Light-off
0
20 40 60 80 100 120 140
Time (min)
Figure 6. Time-dependent relative dielectric constant (εr′) profiles of trilayered sample 3–1
at the frequency range of 1.0‒4.0 GHz under illumination using a LED white light, showing
large photoswitchable amplification of εr′ at the light-off state.
3. Experimental Section
3.1. Materials
Reagents and solvents: aluminum chloride, 1,2-dichloroethane, α-bromoacetyl bromide, sodium sulfate,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), FeCl3·6H2O, FeCl2·4H2O, sodium acetate, n-octylamine,

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1,2-hexadecanediol, 1-oleylamine, 1,2-propanediol, sodium oleate, 1-oleic acid, 1-octadecene, Au(ac)3,
hydrogen tetrachloroaurate(III) trihydrate (HAuCl4·3H2O), phenyl ether, tetramethylammonium hydroxide,
1-octanethiol, and hydroxylamine hydrochloride were purchased from Aldrich Chemicals (St. Louis,
MO, USA) and used without further purification. All other chemicals were purchased from Acros
Chemicals Ltd. (New Brunswick, NJ, USA). The anhydrous grade solvent of THF was refluxed over
sodium and benzophenone overnight and distilled under reduced pressure (10−1 mmHg).
3.2. Spectroscopic Measurements
13
1H-NMR and C-NMR spectra were recorded on either an Avance Spectrospin–200 or AC-300
spectrometer (Bruker, Billerica, MA, USA). UV-vis spectra were recorded on a U-3410 UV spectrometer
(Hitachi, Chiyoda, Tokyo, Japan). Infrared spectra were recorded as KBr pellets on a 750 series FT-IR
spectrometer (Thermo Scientific Nicolet, Waltham, MA, USA). Photoluminescence (PL) spectra were
measured using PTI Fluorescence Master Systems (Photon Technology International, Edison, NJ, USA)
connected with a photomultiplier (914 Photomultiplier Detection System) with a xenon short arc lamp
as the excitation source. Mass spectroscopic measurements were performed by the use of positive ion
matrix-assisted laser desorption ionization (MALDI–TOF) technique on a M@LDI-LR mass spectrometer
(Micromass, Cary, NC, USA). The sample blended or dissolved in the matrix material was irradiated by
nitrogen UV laser at 337 nm with 10 Hz pulses under high vacuum. Mass ion peaks were identified for
the spectrum using the MassLynx v4.0 software. In a typical experiment, the samples of 5, 6, and 7, were
dissolved in CHCl3 in a concentration of 1.0 mg/mL. The matrix of 3,5-dimethoxy-4-hydroxycinnamic
acid (sinapic acid) was dissolved in THF in a concentration of 10 mg/mL. The solution of matrix (1.0 mL)
was taken and mixed with the sample solution (0.1 mL) prior to the deposition on a stainless-steel MALDI
target probe. It was subsequently dried at ambient temperature.
3.3. Synthetic Procedures
Synthesis of 7-α-Bromoacetyl-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene BrDPAF-C9 (6).
A similar method as that of a recently reported procedure was used [14].
Synthesis of 7-(1,2-Dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-di(3,5,5-trimethylhexyl)-2-
diphenylaminofluorene, Monoadduct C60(>DPAF-C9) (1) and Bisadduct, C60[methanocarbonyl-7-
(9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene)]2, C60(>DPAF-C9)2 (2). A similar method as
that of a recently reported procedure was used [14]. Spectroscopic data of 2: FAB+‒MS calcd for
1H11014N2 O2 m/z 1970.8; found, m/z 1971; MALDI−MS (TOF) found, m/z 1974, 1973, 1972, 1971
12
16
C
150
(M+), 1347, 1346, 870, 861, 710, 705, 672, 666, 630, 629, 612, and 583; UV-vis (CHCl3, 2.0 × 10‒5 M)
λmax (ε) 255 (1.9 × 105), 310 (1.1 × 105), and 406 nm (8.5 × 104 L/mol-cm); FT-IR (KBr) νmax 3429 (br),
3163, 2951 (s), 2922, 2863, 1680, 1595 (vs), 1492 (vs), 1465, 1420, 1400, 1316(w), 1277, 1200, 1156
(w), 1093, 1030 (w), 816 (w), 753, 670 (s), and 527 (s) cm‒1; 1H-NMR (500 MHz, CDCl3, ppm) δ 8.5−8.1
(m, 4H), 7.9−7.4 (m, 4H), 7.24 (m, 12H), 7.12 (m, 8H), 7.05 (m, 4H), 5.8−5.3 (m, 2H), 2.1−1.8 (m, 8H),
13
1.35−1.15 (m, 8H), and 1.1−0.5 (m, 60H). C-NMR (500 MHz, CDCl3, ppm) δ 189.8, 154.1, 151.8,
151.7, 149.4, 148.1, 148.0, 147.7, 147.5, 146.9, 146.8, 146.6, 146.2, 146.0, 145.9, 145.7, 145.5, 145.0,
145.0, 144.9, 144.8, 144.7, 144.5, 144.3, 144.0, 143.9, 143.7, 143.6, 143.3, 143.3, 143.1, 143.0, 143.0,
142.9, 142.6, 142.5, 142.3, 142.3, 142.2, 142.1, 140.9, 140.5, 140.0, 139.8, 139.7, 139.5, 134.5, 134.0,

Molecules 2015, 20
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129.8, 129.5, 129.3, 128.65, 124.9, 123.6, 122.3, 119.6, 118.5, 73.4, 73.2, 55.6, 51.3, 51.2, 44.4, 44.4,
42.9, 38.2, 38.2, 38.1, 33.6, 33.5, 33.5, 31.4, 30.4, 29.9, 27.7, 23.1, and 22.9.
3.3.1. Synthesis of γ-FeOx (1.0 < x < 1.5) Nanoparticles
Method A1. In a typical reaction, a mixture of FeCl3·6H2O (2.70 g, 0.010 mol), FeCl2·4H2O
(1.98 g, 0.010 mol), sodium acetate (4.92 g, 0.060 mol, as a hydrolyzing agent), H2O (4.0 mL), and
n-octylamine (7.3 mL, as a capping agent) in 1,2-propanediol (66 mL) were prepared and stirred under
reflux at 150 °C for a period of 5.0 h. It was followed by precipitation upon the addition of 2-propanol
to afford the product in a nearly quantitative yield. Spectroscopic data: FT-IR (KBr) νmax 2970 (w), 2924
(s), 2852 (m), 1743 (w), 1630 (s), 1458 (m), 1383 (m), 1134 (m), 1041 (m), 922 (w), 879 (w), 839 (w),
627 (vs), and 584 (vs) cm‒1.
Method A2. Iron oleate was firstly prepared by heating iron chloride, FeCl3·6H2O (5.4 g, 20 mmol)
and FeCl2·4H2O (2.0 g, 10 mmol), and sodium oleate (36.5 g, 120 mmol) at 70 °C in a mixture solvent,
composed of ethanol (80 mL), distilled water (60 mL), and hexane (140 mL), for a period of 4.0 h.
At the end of reaction, the upper organic layer containing the iron oleate complex was washed three
times with distilled water (30 mL each), dried over sodium sulfate, and solvent evaporated off to yield
iron oleate complex in a waxy solid form. To this resulting organometallic complex, 1-oleic acid (4.3 g,
15 mmol) and 1-octadecene (200 g, act as the solvent) were added at room temperature and refluxed at
320 °C for 1.5 h. Upon the temperature reaching 320 °C, a severe exothermic reaction occurred with the
initial transparent solution turning to turbid and brownish black. The product mixture was cooled to room
temperature, followed by precipitation with ethanol (500 mL). Resulting nanoparticles were collected
using a permanent magnet, washed twice with both 2-propanol (100 mL) and ethanol (100 mL). They
were re-dispersed in nonpolar solvent, such as hexane and toluene, via ultrasonication. In general, dark
solid particles of γ-FeOx (Fe3O4) obtained by this method were found to be highly magnetic in response
to the external magnet and soluble in many nonpolar organic solvents. Distribution of the particle size is
fairly homogenous and was measured via TEM as ~20 nm in diameter on average. Spectroscopic data:
FT-IR (KBr) νmax 2960 (w), 2921 (s), 2852 (m), 1618 (s), 1459 (w), 1407 (m), and 578 (vs) cm‒1.
3.3.2. Synthesis of Au-Nanoparticles Coated γ-FeOx Nanoparticles, γ-FeOx@AuNP
Method B1. Our first trial was involving the direct reduction and deposition of gold acetate, Au(ac)3,
on the surface of iron oxide NPs (10‒20 nm, prepared by either methods A1 or A2) in the presence of
1,2-hexadecanediol and 1-oleylamine. Briefly, to the suspension of γ-FeOx NPs (0.1 g) in phenyl ether
(20 mL) was added Au(ac)3 (0.45 g, 1.2 mmol), 1,2-hexadecanediol (3.0 g, 25 mmol), and oleylamine
(4 mL) under N2 atmosphere. The mixture was heated to 180‒190 °C with vigorously stirred for 2.0 h
while maintain the temperature constant. After cooling to room temperature, the NPs were collected by
a permanent magnet, washed twice with both 2-propanol (100 mL) and ethanol (100 mL). Subsequently,
the NPs were collected with a permanent magnet to yield a dark brown solid powder.
Method B2. To the γ-FeOx nanoparticles (prepared by the method A1 stated above, 100 mg) was added
D.I. water (100 mL) and tetramethylammonium hydroxide (1.0 M, 10 mL, 10 mmol). The mixture was
ultrasonicated for 1.0 h to dissolve particles and yield a transparent brown solution. The solution was
filtered through 0.4-μm PTFE syringe filter to remove insoluble large particles. The solution was then

Molecules 2015, 20
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diluted to 2.0 L by D.I water, added by sodium citrate (0.5 M, 100 mL, 50 mmol), and stirred for 30 min
at ambient temperature. While kept stirring, the solution of hydroxylamine hydrochloride (1.0 M, 2.0 mL,
2.0 mmol) and hydrogen tetrachloroaurate(III) trihydrate (HAuCl4·3H2O, 0.025 M, 2.0 mL, 0.05 mmol)
were added portionwise in 1/10 quantity each by an interval period of 15 min. After finishing addition,
a magnet was used to separate and remove the particles containing γ-FeOx from the solution. They were
washed with D.I water (×2) and ethanol (×2) and, finally, washed with methanol and decanted the
supernatant. The suspension solution was then added acetone (10 mL), methanol (10 mL), and 1-octanethiol
(1.0 mL) and ultrasonicated for 1.0 h to replace hydrophilic stabilizer (tertiary amine or sodium citrate)
on the surface by hydrophobic thiol hydrocarbons. The resulting solids were filtered and washed by water
and ethanol to remove remaining residual hydrophilic stabilizers and excessive 1-octanethiol to yield
core-shell Au-NPs coated γ-FeOx nanoparticles. Spectroscopic data: FT-IR (KBr) νmax 2958 (m), 2928 (s),
2852 (m), 1724 (w), 1626 (s), 1496 (m), 1463 (s), 1380 (m), 1330 (w), 1263 (w), 1168 (m), 1130 (s),
1078 (s), 877 (w), 804 (m), 730 (s), 696 (m), 609 (m), 584 (s), and 557(m) cm‒1.
3.3.3. Preparation of C60(>DPAF-C9)-Encapsulated γ-FeOx@Au Trilayered Core-Shell Nanoparticles,
(γ-FeOx@AuNP)@[C60(>DPAF-C9)]n
We carried out an encapsulation procedure by dissolving γ-FeOx@AuNP nanoparticles (100 mg) in
toluene with the aid of a small quantity of 1-octanethiol, followed by the addition of C60(>DPAF-C9)
(100 mg) and subsequent sonication for a period of 30 min. After filtration of the solution through celite,
an excessive amount of C60(>DPAF-C9) (est. in <5 mg) remaining in the solution was removed. All
encapsulated magnetic nanoparticles filtered off at the top celite surface as brown solids were recovered
by toluene extraction and physically removed from the solution by an internal permanent magnet. Solids
were washed repeatedly by ethanol and ether, followed by drying in vacuo.
Alternatively, a modified method was used to prevent the possible material loss during celite filtration.
In this procedure, both γ-FeOx@AuNP nanoparticles (100 mg) and C60(>DPAF-C9) 1 or C60(>DPAF-C9)2
2 in a predefined weight ratio amount were dissolved in toluene (30 mL) with stirring for 30 min and then
ultrasonicated for an additional more than 30 min until a clear solution being obtained to homogenize
nanoparticles dispersion and increase their interactions with 1 or 2. The solution was concentrated via rotary
evaporation to less than 3.0 mL in volume to increase the molecular contact of 1 or 2 to γ-FeOx@AuNPs.
It was then diluted by toluene again to a volume of 30 mL with stirring and subsequent sonication for
10 min to dissolve excessive 1 or 2. All encapsulated magnetic nanoparticles were physically removed
from the container solution with the assistance of an internal permanent magnet. The nanoparticles were
washed repeatedly by ethanol and ether, followed by drying in vacuo to afford dark brown solids of
(γ-FeOx@AuNP)@[C60(>DPAF-C9)x]n (x = 1 or 2) 3. Spectroscopic data of 3–1 prepared based on the
nanoparticle methods A1 and B2: FT-IR (KBr) νmax 2952 (m), 2920 (s), 2848 (m), 1741 (m), 1675 (m),
1637 (m), 1618 (m), 1591 (s), 1490 (m), 1458 (s), 1429 (m), 1382 (m), 1271 (m), 1203 (s), 1168 (m),
1110 (m), 1076 (m), 1029 (m),.875 (w), 811(w), 748 (m), 694 (m), 617 (m), 582 (s), and 526 (s) cm‒1.
3.4. Tunneling Electron Microscopic (TEM) Measurements
Both formvar and carbon-copper film grids in a 200-mesh size were used for the topography
investigation of molecularly assembled structures, derived from 1 and 2, by TEM images. Samples were

Molecules 2015, 20
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prepared by direct coating the grid with a sample solution of 1.0 × 10−6 M diluted from the master
nanoparticle solution (5.0 × 10−4 M in H2O). Different concentrations (10−4–10−6 M) may be used and
evaluated to ensure full separation of particles from each other without stacking prior to the collection
of microimages. It was followed by the freeze-dry technique via placing the sample-coated grid on a
metal dish that was in thermal equilibrium with liquid nitrogen. This apparatus was then placed inside a
vacuum chamber for overnight to remove all solvents completely prior to the measurement that will
retain the nanoparticle shape on the grid. To prevent particle aggregations during the solvent removal
procedure, a low concentration of 10−5–10−6 M in either H2O or benzene is essential.
3.5. Dielectric and Permittivity Measurements
Dielectric property measurements were carried out by an Agilent Network Analyzer (Agilent
Technologies, Inc., Santa Clara, CA, USA) equipped with an open-ended Agilent 85070E dielectric probe
kit (200 MHz to 50 GHz). Calibration was conducted by using open-ended, close-ended, and attenuated
calibrators prior to each measurement to remove the cable-related instability and system drift errors. In
the experiment, a complex scattering parameter, defined as S11, was measured and converted to relative
complex electric dielectric constant values using Agilent 85071E Materials Measurement Software. This
complex form is compdose of a real and an imaginary part. The former represents the value of dielectric
constant and the latter is defined as the loss factor.
Two light sources were used in the measurement including a LED white light with the output power of
2.0 W and a UVB-enhanced visible lamp (Uvitron 400 W with the output power density of 20 mW/cm2).
Poly(dimethylsiloxane) (PDMS, 1.0 g) semi-solid was applied as a polymer matrix host that is capable
of forming a paste-like sample with 2. A mixture of PDMS and either C60(>DPAF-C9), γ-FeOx NPs,
γ-FeOx@AuNPs, or (γ-FeOx@AuNP)@[C60(>DPAF-C9)]n (100 mg) was prepared by dissolving both
components in ethyl acetate (20 mL) in the testing tube under sonication until a clear solution was obtained.
Ethyl acetate was then completely evaporated under vacuum to yield brown paste-like semi-solid materials.
A custom-built chamber was applied for permittivity measurements to be conducted under a
circumferentially uniform illumination environment. It was achieved by the installation of a reflective
half-circular aluminum plate at the back-wall side surrounding the testing tube which is located at the
center of the chamber. A light was allowed to pass through a small window at the front side of the chamber
to irradiate the sample tube. Reflected light beams were design to refocus from the back-side aluminum
mirror plate back to the tube. Four fans were installed at the top and side-walls of the chamber to control
and prevent temperature building-up inside the chamber. Illumination periods were chosen to be 10, 30,
and 60 min.
4. Conclusions
We design and synthesized several analogous nanomaterials by sequential construction of three-layered
core-shell (γ-FeOx@AuNP)@[C60(>DPAF-C9)1or2]n 3 nanoparticles. These NPs consisting of an
electron-polarizable, bilayered fullerosome membrane located at the outer layer of a NP were fabricated
by the attachment of photoresponsive C60(>DPAF-C9)1or2 molecules on highly magnetic core-shell
γ-FeOx@AuNPs. Highly e‒-polarizable fullerosome of 3 was found to be capable of producing a
‒
charge-separated state of 1 as C60 ·(>DPAF+·-C9) that causes a large amplification of material permittivity.

Molecules 2015, 20
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The observed phenomena are also associated with the photoswitching effect in the frequency range of
0.5‒4.0 GHz. Apparently, multilayered synthetic construction of a core-shell NPs makes inter-layer
interactions much more effective in a near field of direct contact. This allows photoinduced accumulative
plasmon resonance energy in the gold layer to effect Förster resonance energy transfer (FRET) to the
partially bilayered fullerosome membrane shell layer without producing much radiation heat. The
occurrence was followed by the relaxation of both εr′ and εr′′ back to their original values that revealed
an excellent recyclability. We suggest that fullerosomic array of C60 cages in the solid state may be
useful in providing a pathway and mechanism for long-lived charge-delocalized (C60>)n− (n ≥ 1) charges
among nanocages in the nanomembrane, leading to large permittivity increases.
Acknowledgements
The authors at UML thank the financial support of Air Force Office of Scientific Research (AFOSR)
under the grant number FA9550-09-1-0380 and FA9550-14-1-0153.
Author Contributions
All authors contribute a significant effort on this work. M.W. carried out the main synthetic works,
spectroscopic characterization, data analysis, and permittivity measurements; S.J. developed the synthetic
nanoparticle methods; C.S. and T. Y. setup the permittivity and reflectivity measurements and carried out
dielectric properties conversion; T.Y., L.S.T. and L.Y.C. initiated the project, participated in the discussion
of experiment studies, and contribute to a part of manuscript writing; All authors read and approved the
final manuscript.
Conflicts of Interest
The authors declare no conflicts of interest.
References
1. Pillai, S.; Green, M.A. Plasmonics for photovoltaic applications. Sol. Energy Mater. Sol. Cells 2010,
94, 1481–1486.
2. Losurdo, M.; Giangregorio, M.M.; Bianco, G.V.; Sacchetti, A.; Capezzuto, P.; Bruno, G. Enhanced
absorption in Au nanoparticles/a-Si:H/c-Si heterojunction solar cells exploiting Au surface plasmon
resonance. Sol. Energy Mater. Sol. Cells 2009, 93, 1749–1754.
3. Coronado, E.A.; Ezequiel, R.E.; Stefani, F.D. Optical properties of metallic nanoparticles:
Manipulation light, heat and forces at the nanoscale. Nanoscale 2011, 3, 4042–4059.
4. Muhlschlegel, P.; Eisler, H.J.; Martin, O.J.F.; Hecht, B.; Pohl, D.W. Resonant optical antennas.
Science 2005, 308, 1607–1609.
5. Novotny, L.; van Hulst, N.F. Antennas for light. Nat. Photon. 2011, 5, 83–90.
6. Curto, A.G.; Taminiau, T.H.; Volpe, G.; Kreuzer, M.P.; Quidant, R.; van Hulst, N.F. Multipolar
radiation of quantum emitters with nanowire optical antennas. Nat. Commun. 2013, 4, 1‒7.
7. Ditlbacher, H.; Hohenau, A.; Wagner, D.; Kreibig, U.; Rogers, M.; Hofer, F.; Aussenegg, F.R.;
Krenn, J.R. Silver nanowires as surface plasmon resonators. Phys. Rev. Lett. 2005, 95, 257403.

Molecules 2015, 20
14760
8. Bharadwaj, P.; Deutsch, B.; Novotny, L. Optical Antennas. Adv. Opt. Photonics 2009, 1, 438–483.
9. Sau, T.K.; Murphy, C.J. Room temperature, high-yield synthesis of multiple shapes of gold
nanoparticles in aqueous sSolution. J. Am. Chem. Soc. 2004, 126, 8648‒8649.
10. Jana, N.R.; Gearheart, L.; Murphy, C.J. Wet chemical synthesis of high aspect ratio cylindrical gold
nanorods. J. Phys. Chem. B 2001, 105, 4065–4067.
11. Kulkarni, N.; Muddapur, U. Biosynthesis of metal nanoparticles: A review. J. Nanotechnol. 2014,
510246, doi:10.1155/2014/510246.
12. Burda, C.; Chen, X.; Narayanan, R.; El-Sayed, M.A. Chemistry and properties of nanocrystals of
different shapes. Chem. Rev. 2005, 105, 1025–1102.
13. Padmawar, P.A.; Canteenwala, T.; Verma, S.; Tan, L.S.; He, G.S.; Prasad, P.N.; Chiang, L.Y.
Synthesis of C60-diphenylaminofluorene dyads with two-photon absorbing characteristics. Synth. Met.
2005, 154, 185–188.
14. Padmawar, P.A.; Canteenwala, T.; Tan, L.S.; Chiang, L.Y. Synthesis and characaterization of
two-photon absorbing diphenylaminofluorenocarbonyl-methano[60]fullerenes. J. Mater. Chem.
2006, 16, 1366–1378.
15. Padmawar, P.A.; Rogers, J.O.; He, G.S.; Chiang, L.Y.; Canteenwala, T.; Tan, L.S.; Zheng, Q.;
Lu, C.; Slagle, J.E.; Danilov, E.; et al. Large cross-section enhancement and intramolecular energy
transfer upon multiphoton absorption of hindered diphenylaminofluorene-C60 dyads and triads.
Chem. Mater. 2006, 18, 4065–4074.
16. Luo, H.; Fujitsuka, M.; Araki, Y.; Ito, O.; Padmawar, P.; Chiang, L.Y. Inter- and intramolecular
photoinduced electron-transfer processes between C60 and diphenylaminofluorene in solutions.
J. Phys. Chem. B 2003, 107, 9312–9318.
17. El-Khouly, M.E.; Anandakathir, R.; Ito, O.; Chiang, L.Y. Prolonged charge-separated states of
Starburst tetra(diphenylaminofluoreno)[60]fullerene adducts upon photoexcitation. J. Phys. Chem. A
2007, 111, 6938–6944.
18. Elim, H.I.; Anandakathir, R.; Jakubiak, R.; Chiang, L.Y.; Ji, W.; Tan, L.S. Large
concentration-dependent nonlinear optical responses of starburst diphenylaminofluorenocarbonyl
methano[60]fullerene pentaads. J. Mater. Chem. 2007, 17, 1826–1838.
19. Verma, S.; Hauck, T.; El-Khouly, M.E.; Padmawar, P.A.; Canteenwala, T.; Pritzker, K.; Ito, O.;
Chiang, L.Y. Self-assembled photoresponsive amphiphilic diphenylaminofluorene-C60 conjugate
vesicles in aqueous solution. Langmuir 2005, 21, 3267–3272.
20. Yong, V.; Hahn, H.T. Synergistic effect of fullerene-capped gold nanoparticles on graphene
electrochemical supercapacitors. Adv. Nanopart. 2013, 2, 1–5.
Sample Availability: Samples of the compounds 1 and 2 are available from the authors.
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