LETTERS

PUBLISHED ONLINE: 7 DECEMBER 2015 | DOI: 10.1038/NMAT4490

The classical and quantum dynamics of molecular

spins on graphene
Christian Cervetti1*, Angelo Rettori2, Maria Gloria Pini3, Andrea Cornia4, Ana Repolls5,
Fernando Luis5, Martin Dressel1, Stephan Rauschenbach6, Klaus Kern6,7, Marko Burghard6
and Lapo Bogani1,8*
Controlling the dynamics of spins on surfaces is pivotal to
the design of spintronic1 and quantum computing2 devices.
Proposed schemes involve the interaction of spins with
graphene to enable surface-state spintronics3,4 and electrical
spin manipulation411 . However, the influence of the graphene
environment on the spin systems has yet to be unravelled12 .
Here we explore the spingraphene interaction by studying
the classical and quantum dynamics of molecular magnets13 on
graphene. Whereas the static spin response remains unaltered,
the quantum spin dynamics and associated selection rules are
profoundly modulated. The couplings to graphene phonons, to
other spins, and to Dirac fermions are quantified using a newly
developed model. Coupling to Dirac electrons introduces a
dominant quantum relaxation channel that, by driving the spins
over Villains threshold, gives rise to fully coherent, resonant
spin tunnelling. Our findings provide fundamental insight into
the interaction between spins and graphene, establishing the
basis for electrical spin manipulation in graphene nanodevices.
Carbon-based spintronics offers the means to manipulate
localized spins in the close proximity of a carbon nanotube1416 or
graphene sheet411 . This task requires understanding and tuning
the interaction between the components, to minimize quantumdecoherence16 , and to enable spin manipulation17 , for example,
by controlling either the magnetic anisotropy18 or the electronic
coupling5,19 . Here, we exploit the exceptionally clean13 magnetic
features of single-molecule-magnets (SMMs) to explore how spins
interact with graphene substrates.
The grapheneSMM hybrids are obtained by non-covalent
grafting of [Fe4 (L)2 (dpm)6 ], (Hdpm=dipivaloylmethane and
H3 L=2-hydroxymethyl-2-(4-(pyren-1-yl)-butoxy)methylpropane1,3-diol, Fig. 1a; ref. 20) via solution-based assembly on exfoliated
graphene sheets. The two pyrene groups serve as anchors20 to
the graphene sheet. Functionalization of both solid-supported
and bulk dispersions of graphene layers (Methods) allows one
to determine the aggregation behaviour of the molecules on the
surface and perform magnetization measurements on statistically
relevant samples.
Atomic force microscopy (AFM) confirms successful decoration
of graphene by [Fe4 (L)2 (dpm)6 ] (Fig. 1b). Similar coverage was
observed for single- and multi-layer graphene. Sufficiently low

concentrations of [Fe4 (L)2 (dpm)6 ] (C < 106 M) ensure decoration

by individual molecules without appreciable aggregation, whereas a
full layer is formed for C > 105 M (Supplementary Information).
Multiple techniques evidence that the deposited SMMs are
structurally and electronically intact. In particular, the height
distribution in AFM images peaks at 1.8 0.3 nm (Fig. 1c), in close
agreement with the size of a single [Fe4 (L)2 (dpm)6 ] molecule20 . In
addition, Raman spectra (Fig. 1d) exhibit only a small up-shift of
the graphene G band by 4 cm1 after functionalization, indicating
slight p-type doping21 . This conclusion is supported by the small
positive shift of the charge neutrality point observed in the resistance
versus gate voltage curves (Fig. 1e,f), corresponding to a chargetransfer of only 0.08 e per SMM. Furthermore, X-ray photoelectron
spectra exhibit the same characteristic Fe2p peak positions of thick
films of [Fe4 (L)2 (dpm)6 ] (Supplementary Information) and mass
spectra evidence clear fingerprints of intact [Fe4 (L)2 (dpm)6 ] at 1,919,
1,777 and 1,736 amu (Fig. 1g and Supplementary Information).
The static magnetic properties of the hybrids are
indistinguishable from those of crystalline [Fe4 (L)2 (dpm)6 ]
(Fig. 2). The temperature (T ) dependence of the m T curves (where
m is the static molar magnetic susceptibility, defined as the ratio
between magnetization and the applied magnetic field, M/H )
exhibits the same minimum at 100 K and a maximum around 6 K
(Fig. 2a and Supplementary Information). The M versus H data also
match within experimental error. The characteristic m T versus
T curve can be fitted20 by considering g = 2.00 0.05 and two
intramolecular exchange interactions between nearest-neighbour
and next-nearest-neighbour Fe(III) ions (with exchange constants
JNN = 14.85 0.05 cm1 and JNNN = 0.09 0.05 cm1 , respectively),
in excellent agreement with previous investigations, confirming a
total spin ground state S = 5.
The low-temperature magnetic properties of SMMs are
dominated by the presence of a large magnetic anisotropy13 ,
which partially lifts the degeneracy of the ground multiplet and
creates an energy barrier 1E separating the |ms i and |ms i states
(Fig. 3a). Two spin-relaxation mechanisms are thus possible: a
classical overbarrier process, where multiple phonon absorptions
allow the barrier 1E to be overcome, and a quantum tunnelling
(QT) mechanism, which takes place between degenerate levels at
opposite sides of the barrier13 . QT can be suppressed by applying

1 1. Physikalisches Institut, Universitt Stuttgart, Pfaffenwaldring 57, D-70550 Stuttgart, Germany. 2 Dipartimento di Fisica, Universit di Firenze,
Via G. Sansone 1, I-50019 Sesto Fiorentino, Italy. 3 Istituto dei Sistemi Complessi, CNR, Unit di Firenze, Via Madonna del Piano 10, I-50019 Sesto
Fiorentino, Italy. 4 Dipartimento di Scienze Chimiche e Geologiche, Universit di Modena e Reggio Emilia, INSTM RU, Via G. Campi 183, I-41125 Modena,
Italy. 5 Instituto de Ciencia de Materiales de Aragn, CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, E-50009 Zaragoza, Spain. 6 Max-Planck-Institut
fr Festkrperforschung, Heisenbergstrasse 1, D-70569 Stuttgart, Germany. 7 Institut de Physique de la Matire Condense, Ecole Polytechnique Fdrale
de Lausanne (EPFL), CH-1015 Lausanne, Switzerland. 8 Department of Materials, University of Oxford, 16 Parks Road, Oxford OX1 3PH, UK.
*e-mail: cervetti.christian@gmail.com; lapo.bogani@materials.ox.ac.uk

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NATURE MATERIALS DOI: 10.1038/NMAT4490

LETTERS
a

Si/SiO2

Graphite

45

Pristine

20

R (k)

Before

0.5

nm

1 2 3 4
Height (nm)

After

20
0

nm

Intensity (a.u.)

d
Assembly

Hybrids

1.0

15

103 counts

Graphene

30

17 1,736
12

1,553

1,583

1,613

Raman shift (cm1)

10
20 30 40
Gate voltage (V)

[Fe4(L)2(dpm)6]
1,777
1,919

12 1,736
7

50

1,919

2,124

2
1,760

103 counts

Au
markers

Counts

1.5

1,920
2,080
Mass (amu)

1,916 1,920
Mass (amu)

Hybrids

1,919

1,777

1,919

2
1,760

1,920
2,080
Mass (amu)

1,916 1,920
Mass (amu)

Figure 1 | The graphenespin hybrids. a, Grafting of the molecular magnets on graphene and crystal structure of [Fe4 (L)2 (dpm)6 ] (pyrene groups
highlighted in blue, hydrogens and t-butyl groups omitted). b, AFM images of graphene flakes before and after grafting, at C = 2.5 108 M. c, AFM height
distribution for sub-monolayer coverage and Gaussian fitting, indicating a mean value of 1.8 nm. d, Raman G band, acquired with a 632.8 nm laser at the
centre of an exfoliated graphene flake, before (black) and after (red) functionalization. Lines are fits to the data with single Lorentzian curves. e, Optical
image of the graphene device, with the graphene flake outlined in red. f, Gate dependence of the four-terminal resistance for a single-flake graphene
field-effect transistor, for pristine graphene (black) and after grafting (red), at C = 104 M. Dashed lines highlight the region of constant charge carrier
mobility. g, MALDI-TOF spectra of crystalline [Fe4 (L)2 (dpm)6 ] (top) and of the hybrids (bottom), with zoom-ins on one isotropic pattern shown on the
right. Blue lines are simulations for intact cluster cores.

an external magnetic field H that lifts the degeneracy of the |ms i

levels. This allows one to examine the effect of graphene on both
relaxation mechanisms separately.
The magnetization dynamics is probed by measuring the real ( 0 )
and imaginary ( 00 ) response to a small magnetic field oscillating
at frequency . In a static field H =1 kOe (Fig. 3b), where only
thermally activated behaviour is present, isolated molecules on
graphene show a faster magnetization dynamics than those in
crystalline [Fe4 (L)2 (dpm)6 ], for which Arrhenius analysis yields a
barrier 1E = 9.7 0.7 cm1 . In H = 0 (Fig. 3c), all |ms i and |ms i
sublevels fall back into resonance and QT is activated, thereby
magnifying enormously the difference between the hybrids and
the crystals responses. The T -dependence of the spin-relaxation
time, , (Fig. 4a) shows that for crystalline [Fe4 (L)2 (dpm)6 ] the
thermally activated region persists down to 800 mK, below which
temperature QT sets in. This contrasts strikingly with the spin
relaxation in the hybrids, which is entirely dominated by QT,
and the QT rate is about one million times higher ( 1 = 105 Hz
versus 101 Hz).
To explain these observations we subdivide the spin anisotropy
into different contributions, with each term having the symmetry
of a corresponding tesseral harmonic. This approach produces
an intuitive but rigorous picture of the spin behaviour via
the Hamiltonian:
2S
X
j j
i
H = B SgH +
Bi O
(1)
i2
ji

where the first term describes the Zeeman interaction between the
molecular spin S and H (B is the Bohr magneton, g is the Land
factor) and the second models the spin anisotropy via the spin
ji that correspond to different harmonics, each weighted
operators O
j
by a coefficient Bi . These operators, called Stevens operatorequivalents13,22 , contain the jth power of the spin ladder operators,
2

S + and S , and the (i j)th power of S z (see Supplementary

Information for explicit expressions and a pictorial representation
of the associated harmonics). With equation (1) we can model
the effect of any external electric field, for example the electron
density of an underlying substrate, by introducing in the sum a
term of corresponding symmetry12,22 and discarding all terms not
belonging to the point group of the spin environment. Stevens
operator-equivalents have an effect on both classical and quantum
ji terms with j = 0 contain powers of S z only,
relaxation channels: O
and contribute to 1E but do not mix the |ms i eigenstates; terms with
j 6= 0, in contrast, mix states differing in ms by a multiple of j, opening
the QT relaxation channel.
For crystalline [Fe4 (L)2 (dpm)6 ], the Hamiltonian (1) reads
02 + B22 O
22 + B04 O
04 + B34 O
34 + B SgH , and electron paramagH = B02 O
netic resonance (EPR) studies yield20 B02 = 0.136 0.003 cm1 ,
B22 = 8.1 0.7 103 cm1 , B04 = 2.4 0.5 105 cm1 and
g = 2.000 0.005. B02 being the leading j = 0 term, 1E
= 3|B02 |S2 ,
whereas multiple spectroscopic and magnetic investigations
on related systems determined B34 to be <5 1 104 cm1 .
By using g = 2.004 0.003 and B02 = 0.12 0.02 cm1 , the
magnetization curves of both hybrids and crystals (Fig. 2b) are
perfectly reproduced. Moreover, the barrier value extracted from
the dynamics provide B02 = 0.13 0.01 cm1 , again leading to an
excellent overall agreement for the leading anisotropy term. Axial
distortion of the SMMs on graphene can thus be excluded.
We now discuss how the graphene environment alters the spin
relaxation (Fig. 4b). Dipolar and hyperfine interactions introduce
a local dynamic magnetic field distribution that alters the QT
rate by broadening the QT resonances13,23 (Fig. 3a). The widths
of these distributions, as determined23,24 from dilution and nuclear
resonance experiments in crystals, are 200 and 1 Oe, respectively.
In the hybrids, intermolecular dipolar interactions are strongly
reduced owing to the sizeable separation between the molecules and
magnetic shielding by graphene, which is predicted to be extremely

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NATURE MATERIALS DOI: 10.1038/NMAT4490

a

LETTERS
a

10

I0

|1

|1

|2
QT

Wn

|3

Energy (cm1)

|3

QT

|4
Phonons

12

|2

100

150

200

250

T (K)

10

5K

2.5 K

1.8 K
90

(103 e.m.u. mol1)

Mm (NAB)

6
4
2
10
20
HT1 (k Oe K1)

10 20 30 40
HT1 (k Oe K1)

Figure 2 | Static magnetic properties of the hybrids. a, Temperature

dependence of the m T product for [Fe4 (L)2 (dpm)6 ]20 (triangles) and the
hybrids (circles) (measured in H = 1 kOe for the hybrids and H = 1 kOe below
30 K and in 10 kOe above 30 K for the crystals). The black line represents
fitting by considering the intact [Fe4 (L)2 (dpm)6 ] core (see text and ref. 20).
b, Comparison of the low-temperature magnetization curves of crystalline
[Fe4 (L)2 (dpm)6 ] (solid circles) and the graphene hybrids (open circles),
showing the molar magnetization (Mm ) versus H/T curves acquired at 5 K
(left), 2.5 K (middle) and 1.8 K (right) after subtracting the graphene matrix
contribution and rescaling by the number of [Fe4 (L)2 (dpm)6 ] molecules.
Solid lines are fits to the data (see text and ref. 20).

efficient25 . In contrast, hyperfine interactions arise from the nuclei

inside the molecules themselves, and are unaffected by the substrate.
Overall, this imposes an intrinsic upper limit of 10 Hz to the
QT rate of isolated [Fe4 (L)2 (dpm)6 ] (Fig. 4a; refs 13,23,24). Any
additional acceleration of QT must arise from interactions with the
graphene layer.
To evaluate the effect of graphene vibrations, we extend the established theoretical framework26,27 to two-dimensional phonon baths
(Supplementary Information). In principle, the effect of phonons on
each molecular group is to induce a time-dependent modification
(or modulation) of any term of the magnetic energy. However, it
can be shown13 that, at low temperatures, the modulation of the
isotropic exchange does not induce transitions between the |ms i
sublevels of the lowest exchange multiplet. Therefore, as we are interested in temperatures much lower than the Debye temperature, the
only significant contribution will arise from the modulation of the
anisotropy energy induced by long-wavelength acoustic phonons.
The transition probabilities can be obtained26,27 by adding to equation (1) the spinphonon perturbation term
s
X
~

Vq, (S)(Cq, Cq,

)
Hsp = i
2m

c
q,
q,
where , q and are the phonon frequency, wavevector and
polarization, ~ the Planck constant, mc the unit cell mass, Vq, the
spinphonon interaction potential, and Cq, the phonon creation

(103 e.m.u. mol1)

90

()

5
10
HT1 (k Oe K1)

|5

90

0
0

QT

|5

(Hz)

1,000
H = 1 kOe

Crystals

10

1.7

(103 e.m.u. g1)

50

(Hz)

170,000
H=0

30
Crystals

20
10
0

(103 e.m.u. g1)

|4

Hyperfine

mT (e.m.u. K mol1)

15

Hybrids

3
T (K)

0.2
Hybrids
0.0

T (K)

Figure 3 | Classical and quantum magnetization dynamics. a, |ms i

sublevels of the ground state of the single-molecule-magnet
[Fe4 (L)2 (dpm)6 ], as obtained from equation (1). Absorption of phonons
allows the barrier to be thermically overcome (green arrows). W n
indicate the transition probabilities between magnetic |mi states induced
by the absorption (+) or emission () of n phonons. Quantum tunnelling
happens between admixed levels (red arrows), whereas hyperfine and
dipolar interactions create energy distributions (orange). Interaction with
Dirac electrons increases the tunnel splittings below |3i and |3i (red
areas, exaggerated for clarity). b, Temperature and frequency dependence
of the imaginary component of the dynamic susceptibility ( 00 ) in a
magnetic field H = 1 kOe for [Fe4 (L)2 (dpm)6 ] (top) and hybrids with
isolated molecules (bottom). Lines are simulations with the theory (see
text for the theory). c, Temperature and frequency dependence of the real
component of the dynamic susceptibility ( 0 ) in H = 0 for [Fe4 (L)2 (dpm)6 ]
(top) and hybrids with isolated molecules (bottom). Lines are simulations
with the theory (see text for the theory).

operator, with the sum running over the Brillouin zone. For intact
molecules, similar local distortions are expected in both crystals
and hybrids; namely, provided that B02 is essentially unaltered, as
in the present case, Vq, will also be similar in both materials.
In contrast, the different phonon densities of three- and twodimensional baths will strongly alter the relaxation dynamics. For
the hybrids, the relevant phonon bath can be described by the longwavelength spectrum of the acoustic branches of graphene, which
has an analytical expression21 . Under these assumptions we obtain
(see Supplementary Information) the following relation:

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Rc 2 h kB Ch4
=
Rh 3 c } Cc5

(2)
3

NATURE MATERIALS DOI: 10.1038/NMAT4490

LETTERS

Dipolar

m
(n
kx

0
10
10

Hyperfine and dipolar

1 )

(s)

Graphene phonons
Hyperfine

15 0 15
ky (nm1)

Electrons

Field
distribution

|mS

|mS
T (K)

cm
3 (
B4

I n coh

102

e re

M ix

1
20
4 4

1 )

1.0

EF

0.1

(n
kx

107

105

(s)

path

Hybrids

1 )

100

|mS Adiabatic |mS

Diabatic
path

Hybrids

nt

Crystals

103

Crystals

4
0
1
ky (nm )

ed

im

101

1,600

Phonons

Vi l l a s r
in

eg

E (cm1)

5.0
T(
K) 1.0
0.2

Figure 4 | Contributions to the zero-field spin dynamics. a, Temperature dependence of the spin-relaxation time in H = 0 for [Fe4 (L)2 (dpm)6 ] (blue
triangles) and the hybrids (red circles). Lines show the curves for a 0.3 Hz tunnelling frequency (blue), and the estimations of suppressed dipolar
interactions (orange), graphene phonons (green) and Dirac electronsspin interactions (red). b, Different contributions to relaxation lifetime of spins on
graphene: the dipolar and hyperfine interactions produce dynamic field distributions around all avoided level crossings (orange); transition probabilities are
determined by the graphene phonon dispersion (green surface); Dirac electrons (red surface) introduce quantum mixing terms with fingerprint symmetry.
3
c, Representation of the resulting magnetic anisotropy for [Fe4 (L)2 (dpm)6 ] and the hybrids, visualizing the B34 O 4 term arising from interactions with Dirac
0
electrons. B2 is decreased tenfold for clarity. d, Different tunnelling regimes, as a function of temperature and of the strength of the perturbative driving
term B34 . The regime experimentally observed for the SMMsgraphene hybrids is highlighted in red.

where c and h subscripts denote crystals and hybrids, R is a

parameter proportional to the experimentally observable phononinduced relaxation rate, the mass density, C the sound velocity and
kB the Boltzmann constant. This model provides excellent agreement with the data at H 6 = 0, where the relaxation is expected to be
dominated by spinphonon interactions (Fig. 3b), simultaneously
accounting for the behaviour in both crystals and hybrids. Notably,
no fitting parameters are necessary, and full, quantitative agreement
j
is attained by using the same set of Bi coefficients and introducing
the known speed of sound of graphene21 , Ch = 2 104 m s1 , for
the hybrids. The behaviour of crystalline [Fe4 (L)2 (dpm)6 ] is restored
in hybrids with large SMM aggregates, for which the vibrational
bath more closely resembles the three-dimensional case (Supplementary Information). These observations underscore the relevance
of graphene vibrational modes for classical spin relaxation.
By contrast, the different phonon bath cannot explain the striking
enhancement of QT at H = 0, which requires coupling to graphene
electrons (Fig. 4a). The latter is expressed, within the formalism
of equivalent Stevens operators13,22 , by including the perturbation
integral hms (M )|VI |G i, where molecular and graphene electronic
states (M and G , respectively) interact via the potential VI , altering
the hms | spin state. The wavefunction G has three-fold symmetry,
and the corresponding point group22 permits non-vanishing integral
j
terms only for Bi coefficients with j a multiple of three, independently of the form of VI . In the perturbation treatment of the spin
graphene interaction, all such terms have an identical effect on the
level mixing and the QT rate of the lowest |ms i levels, differing
only in the perturbation order. To address QT, we merge all terms
into an effective overall graphene effect represented by the leading 34 = B34 bS z (S 3+ + S 3 ) + (S 3+ + S 3 )S z c/4, which directly
order term B34 O
admixes only the ms = 3 states (direct mixing of lower levels
22 ). By introducing a
would require symmetry terms such as B22 O
3
3
1
B4 > 2 10 cm term into the simulations, while maintaining
all other parameters, both the a.c.-susceptibility peak (Fig. 3c)
and the T -dependence of (Fig. 4a) are excellently reproduced.
A pictorial representation of the spin anisotropy in the crystals
4

34
and hybrids highlights the significant weight of the additional O
term and the signature of the three-fold rotational symmetry of
graphene on the spin anisotropy (Fig. 4c). The explicit operator
form of the microscopic interaction potential VI is debated. One
possibility is the Heisenberg form = (S + + S + + 2S z z )/2,
where + , , z are the spin operators of the Dirac fermion; nevertheless the nature of the underlying scattering processes remains
debated. For [Fe4 (L)2 (dpm)6 ], a direct quantitative comparison
among the different proposals is intricate, because of the cumbersome ab initio evaluation of the amplitude cross-sections. Most
importantly, spin-flip processes as efficient as observed for the
hybrids are predicted only when scattering due to the presence
of two K points is included in the theory28 , and the values here
obtained can be used to validate the theoretical models proposed for
spinDirac fermion interactions29 .
Strongly perturbative QT of spins, predicted by Villain decades
ago13 , strictly requires pronounced electronic perturbations combined with minimal dipolar interactions. These conditions are
hard to fulfil in crystals, such that the quantum spin dynamics of
Villains regime has so far eluded observation. Graphene hybrids
offer the ideal conditions by simultaneously suppressing dipolar
interactions and electronically enhancing the transverse anisotropy
terms. For suppressed dipolar fields, weak perturbations lead to a
non-monotonic behaviour in the versus T plot, where standard
tunnelling is followed by a slow descent into Villains QT regime
(Supplementary Information). In contrast, the B34 perturbation term
introduced by graphene is large enough to directly drive the spins
into Villains regime, leading to a monotonous temperature dependence of (Fig. 4d). The associated threshold yields a lower bound
of 0.3 eV for the interaction between SMM spins and the Dirac
electrons, lower than the estimated spinorbit coupling in graphene.
To conclude, our observations set the theoretical and experimental basis for the exploration of the magnetic effects introduced by
localized spins in graphene. The clear role of the vibrational and
electronic interactions, here unravelled, can now be exploited in
the design of spin-nanomechanical and nanospintronic devices. The

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NATURE MATERIALS DOI: 10.1038/NMAT4490

strong graphene-induced terms allow the possibility of coherent
spin manipulation, via electrically tuned spin mixing, and thus
the control of molecular spins in ways hitherto reserved to other
qubits30 . The observed interaction already introduces a spin-level
mixing comparable to those used for qubit manipulations30 , and
the use of molecular magnets with even higher spinorbit coupling
(for example, rare-earths) could enhance such effects even further.
Similar effects, with the same symmetry, can also be envisaged for
other systemsfor example, SMMs on reconstructed Au surfaces19 .
Villains tunnelling regime, being by definition coherent, also opens
novel perspectives for quantum operations. Finally, the observation of substrate effects on the quantum dynamics constitutes an
important methodological tool that can be applied to study other
spinsubstrate interactions, providing unique details on symmetrybreaking quantum effects.

Methods
Methods and any associated references are available in the online
version of the paper.
Received 13 August 2014; accepted 5 October 2015;
published online 7 December 2015

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Acknowledgements
We thank J. Wrachtrup and E. Rastelli for discussions; M. Konuma, U. Sttzel, J. Ses,
A. L. Barra, D. Drung, Th. Schurig and L. Sebeke for assistance with the measurements;
and financial support from Italian MIUR, Spanish MINECO (MAT2012-38318-C03-01),
BW-Stiftung (Kompetenznetz Funktionelle Nanostrukturen), ERC-StG-338258
OptoQMol, the Royal Society (URF fellowship and grant) and the AvH Stiftung
(Sofja Kovalevskaja award).

Author contributions
C.C. performed the functionalization and most measurements. A.C. synthetized the
molecules. C.C. and S.R. acquired the MALDI-TOF spectra. A.Repolls and F.L.
performed the ultralow-temperature magnetic measurements. A.Rettori, M.G.P. and L.B.
performed the theoretical analysis. L.B. and M.B. conceived the experiments. L.B. wrote
the draft and all authors contributed to discussions and the final manuscript.

Additional information
Supplementary information is available in the online version of the paper. Reprints and
permissions information is available online at www.nature.com/reprints.
Correspondence and requests for materials should be addressed to C.C. or L.B.

Competing financial interests

The authors declare no competing financial interests.

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NATURE MATERIALS DOI: 10.1038/NMAT4490

LETTERS
Methods
[Fe4 (L)2 (dpm)6 ] was synthesized as previously reported20 . Graphene was
mechanically exfoliated from highly oriented pyrolytic graphite onto
Si/SiO2 substrates. Surface hybrids were obtained by immersion in a
solution of [Fe4 (L)2 (dpm)6 ] in 1,2-dichloroethane:dichloromethane (9/1, v/v)
at room temperature, followed by washing with isopropanol. Bulk samples
of the hybrids were prepared by first sonicating 8.4 mg of graphite powder in
20 ml of the solvent mixture for 48 h, followed by adding 11.5 mg of
[Fe4 (L)2 (dpm)6 ] in 20 ml of the same mixture, followed by stirring for
45 min and final filtering through PTFE membranes (0.2 m pore size).
Magnetic measurements were corrected for the diamagnetism of the sample

and sample holder, as independently determined. An in-house-built micro-SQUID

susceptometer inside a dilution refrigerator was used for zero-field
measurements, with extremely small a.c. field amplitudes (50 mOe) and
the data corrected by the bare graphene signal. AFM images were acquired with a
Bruker Icon system in tapping mode, using Olympus AC200TS cantilevers.
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry
(MALDI-TOF MS) spectra were recorded using a laser pulsed at 4 Hz, whereas
the X-ray photoemission spectroscopy (XPS) spectra were obtained with a
monochromatized Al-K source (1,486.6 eV)see Supplementary Information for
details. Electronic devices were fabricated using a polymethyl methacrylate
(PMMA) resist, e-beam lithography and thermally evaporated Au/Ti.

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