Rational engineering of dimeric Dy-based Single-Molecule Magnets for surface grafting

Article abstract of DOI:10.1016/j.poly.2019.02.040

The deposition of Single-Molecule Magnets (SMMs) on surfaces is a mandatory step toward their possible use as data-storage units or qubits. In this study we report the structural and magnetic characterization of two parent compounds of a well-known SMM called DyPyNO, ([Dy(hfac)₃(PyNO)]₂ with hfac = hexafluoroacetylacetonate and PyNO = pyridine-N-oxide), that are targeted to be deposited on gold surfaces. Thio-substitution of the pyridine ring of these dimers is expected to provide good anchoring group toward deposition on gold. We have investigated two significantly different geometries of the anchoring groups in dimers 1 and 2. Interestingly, despite these strong differences, SMM behavior is remarkably well-preserved in the polycrystalline material offering possibilities to graft these SMMs on surface.

Full text of DOI:10.1016/j.poly.2019.02.040

Accepted Manuscript
Rational engineering of dimeric Dy-based single-molecule magnets for surface
grafting
Xiaohui Yi, Fabrice Pointillart, Boris Le Guennic, Julie Jung, Carole
Daiguebonne, Guillaume Calvez, Olivier Guillou, Kevin Bernot
PII:
S0277-5387(19)30141-X
https://doi.org/10.1016/j.poly.2019.02.040
POLY 13784
DOI:
Reference:
Polyhedron
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Accepted Date:
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19 February 2019
21 February 2019
Please cite this article as: X. Yi, F. Pointillart, B. Le Guennic, J. Jung, C. Daiguebonne, G. Calvez, O. Guillou, K.
Bernot, Rational engineering of dimeric Dy-based single-molecule magnets for surface grafting, Polyhedron (2019),
doi: https://doi.org/10.1016/j.poly.2019.02.040
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Rational engineering of dimeric Dy-based single-molecule
magnets for surface grafting
Xiaohui Yi,a Fabrice Pointillart,a Boris Le Guennic,a Julie Jung,a,b Carole Daiguebonne,a
Guillaume Calvez,a Olivier Guilloua and Kevin Bernot*a
a Univ Rennes, INSA Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) –
UMR 6226, F-35000 Rennes, France
b Los Alamos National Laboratory, Theoretical Division, Los Alamos, NM 87545, USA
Corresponding author: Kevin.bernot@insa-rennes.fr (K. Bernot)
Dedicated to Professor Miguel Julve on the occasion of his 65th birthday, and for its
outstanding contribution to the field of coordination chemistry and molecular
magnetism.
Abstract
The deposition of Single-Molecule Magnets (SMMs) on surfaces is a mandatory step
toward their possible use as data-storage units or qubits. In this study we report the
structural and magnetic characterization of two parent compounds of a well-known
SMM called DyPyNO, ([Dy(hfac)3(PyNO)]2 with hfac = hexafluoroacetylacetonate and
PyNO = pyridine-N-oxide), that are targeted to be deposited on gold surfaces. Thio-
substitution of the pyridine ring of these dimers is expected to provide good anchoring
group toward deposition on gold. We have investigated two significantly different
geometries of the anchoring groups in dimers 1 and 2. Interestingly, despite these
strong differences, SMM behavior is remarkably well-preserved in the polycrystalline
material offering possibilities to graft these SMMs on surface.
Keywords
1

Lanthanides, Sulfured ligands, Single-Molecule Magnets, Dimers, Electrostatics,
Surface.
2

1. Introduction
Single-molecule magnets (SMMs) are molecules able to act as magnets at the
molecular scale.[1, 2] Their unique magnetic behavior can be used in functional
devices, mainly in the field of low-temperature molecular magnetic data storage.[3-6]
The exploitation of SMMs in this area of research requires being able to assemble
them in ordered arrays, where each bit of information can be easily addressed. Thus
technological applications with SMMs as key molecular components will require the
formation of monolayer or thin film coverage on adapted substrates. The two main
routes to do so are physical [7] or chemical deposition. [8, 9] The latter is possibly
more adapted to the formation of monolayers because on-surface auto-organization
of the molecules can occur. Such self-assembled monolayers (SAM) of SMMs were
mainly reported on molecules functionalized by thio-methyl groups in order to graft
them on Au(111) surfaces.[10-13]
Some of us previously reported a series of Dy-based SMMs (called DyPyNO)[14] that
can be physic-sorbed as thick-films on surfaces by sublimation techniques.[15]
Chemical tuning of this molecular platform allows to organize the SMMs in a 3D
molecular material,[16] to optimize their SMM behavior by ligand substitution[17, 18]
and to transfer this enhancement on molecular thick films.[18] It also allows to test
their dependence toward DyIII isotopic substitution [17] and even to produce devices
with electric driven reversible luminescent modulation.[19]
In order to deposit DyPyNO as SAM on gold it has to be substituted by thio-based
groups. However, the magnetic behavior of lanthanide-based SMMs is extremely
sensitive to small geometric molecular changes.[5, 20-30] The objective of this work is
to study the possibility of thio-substitution of DyPyNO and the influence on its SMM
behavior.
Two different ligands were used, with different length and orientation of the anchoring
groups that may provide different grafting ability. First one is 3-methylsulfanyl-pyridine
N-oxide (L1) and reaction with [Dy(hfac)3(H2O)2] (hfac- = hexafluoroacetylacetonate)
provides [Dy(hfac)3(L1)2]2, latter called 1. The second one is 4-methylcarbodithioate-
pyridine N-oxide (L2) and provides [Ln(hfac)3(L2)2]2 latter called 2. This ligand may
3

induce stronger sulfur bonding with the gold surface (two available sulfur atoms) as
well as an enhanced spacing between the gold surface and the hfac- ancillary ligands.
2. Materials and methods
Reagents: All other reagents were purchased from Aldrich Co., Ltd. and used without
further purification.
X-ray crystallography: Single crystals of 1 and 2 were mounted on APEXII AXS Bruker
diffractometer form CDIFX (ISCR diffractometry center). It is equipped with a CCD
camera and a graphite monochromated Mo-Kα radiation source (λ = 0.71073 Å). Data
were collected at 150K. Structure solving was done via direct methods using SIR-97
[31] and refined trough WinGX interface [32] using SHELXL program.[33]
Crystallographic data can be found in supplementary materials. All data were
deposited to the Cambridge Structural Data Base under CCDC 1819460 and CCDC
1819461 for 1 and 2, respectively.
1
NMR: H NMR spectra were recorded with a Bruker Ascend 400 spectrometer.
1
Chemical shifts are reported in parts per million referenced to TMS for H NMR
spectroscopy.
Powder X-ray diffraction: X-ray powder diffractogramms were collected using a
Panalytical X’Pert Pro diffractometer equipped with an X’celerator detector in θ-θ
mode with Cu-Kα (λ = 1.54 Å). The calculated patterns were produced using Mercury
3.0 (Figure S1).
TGA/TDA analysis: Analyses were performed using a PerkinElmer Pyris Diamond
thermal analyzer with a 5°C/min heat rate under N2 atmosphere (100mL.min-1)
Magnetic measurements: Static and dynamic magnetic measurements were
performed on single-crystals picked one by one in the preparation mixtures. They were
then ground and pressed in pellets to avoid crystallite orientations. Measurements
were performed on a Quantum design MPMS magnetometer equipped with a RSO
4

probe. All measurements were corrected from the contribution of the sample holders
and their diamagnetic contribution subtracted according to Pascal’s constants.
Ab-initio calculations: Wavefunction-based calculations were carried out on 1 and 2 by
using the SA-CASSCF/RASSI-SO approach, as implemented in the MOLCAS quantum
chemistry package (see SI for more details).
3. Experimental
Precursor synthesis: Dy(hfac)3(H2O)2 precursor were synthesized according to reported
methods.[34]
Scheme 1. Synthetic scheme for the design of L1 and L2.
3-methylsulfanyl-pyridine N-oxide (L1): 420 mg of 3-nitropyridine-N-oxide were
placed in 2 mL of acetic acid. 3.6 mL of acetyl bromide are added. After 3h of stirring at
80°C, the mixture is cooled at room temperature and then put in ice before
neutralization with NaOH 10 M then Na2CO3. The aqueous phase is extracted four
times with CH2Cl2. The organic phases are combined then dried with MgSO4. After
5

evaporation of the organic solvent under vacuum, the resulting 3-bromopyridine-N-
oxide powder is used for the next step without further purification (Yield: 452 mg, 87
%). The 452 mg of 3-bromopyridine-N-oxide are dissolved in 5 mL of EtOH then an
ethanoic solution of NaCH3S (182 mg) was added. The suspension was stirred under
reflux for 1h, cooled at room temperature and filtered. The filtrate is diluted with
water and extracted with 4×20 mL of Et2O. Finally the residue is purified on alumina
chromatography using a 3:1 CH2Cl2/MeCN eluent to give a colorless powder (yield:
1
275mg, 75%). H NMR: 2.94 (3H, s); 7.68 (1H, dd), 8.09 (2H,m), 8.51 (1H, dt) in DMSO
d6.
N-Oxy-pyridine-4-carbodithioic Acid Methyl Ester (L2): This ligand was obtained
according to the reported experimental procedure.[35]
Complexes synthesis: Compound 1 was obtained using the following procedure: 0.1
mmol of 3-methylsulfanyl-pyridine N-oxide (L1) was dissolved in 10ml of CHCl3 and
added drop by drop to a 10 ml CHCl3 solution of 0.1 mmol of [Dy(hfac)3(H2O)2]. The
resulting solution was stirred at room temperature for five minutes and covered by a
layer of n-heptane. After storing at 2°C for several days single crystal suitable for X-ray
diffraction were obtained. The same procedure was used for the synthesis of 2.
4. Results and discussion
4.1. Crystal structure description
Single-crystal X-ray diffraction measurement on 1 reveals that it crystallizes in
monoclinic P21/n space group. The main structural parameters are listed in Table S1.
The asymmetric unit of the compound is made of one DyIII ion, three hfac-
ligands and one 3-methylsulfanyl-pyridine N-oxide ligand (L1). Its oxygen atom (O7)
links two DyIII ions in a μ2 mode (Figure 1a). A center of inversion is located in the
middle of the double bridge and makes the two DyIII ions equivalent. The Dy-Dy
distance is 4.02(8) Å. Each DyIII is eight coordinated by six oxygen atoms (O1, O2, O3,
O4, O5 and O6) from hfac- ligands and two oxygen atoms (O7) from L1.
6

Figure 1. (a) Representation of 1 (dysprosium, dark green; fluorine, light green; sulfur, yellow; oxygen,
red; carbon, grey) . (b) View of the crystal packing along a axis. (c) and (d) different views of the
coordination environment of the DyIII atom.
The bond lengths of Dy-O(hfac-) are in the range 2.32(6)-2.37(2) Å, while Dy-O(L1)
are 2.38(3) Å (Table S2). CSM analysis [36, 37] shows that the coordination
environment of the DyIII ion is very close to a square antiprism (D4d) geometry (CSM =
0.618) (Figures 1c and 1d and Table S3). The two planes of the square antiprism are
made of O1, O2, O5, O6 and O3, O4, O7, O7 atoms, respectively. Each dimer is well
isolated and the shortest interdimer Dy-Dy distance is 11.17(9) Å (Figure 1b).
Single-crystal X-ray measurement on 2 highlights that it crystallizes in triclinic P-
1 space group. The main structural parameters are listed in Table S4. The substitution
of L1 for 4-methylcarbodithioate-pyridine N-oxide (L2) in the coordination process
affords a very similar dimer (Figure 2).
7

Figure 2. (a) Representation of 2 (dysprosium, dark green; fluorine, light green; sulfur, yellow; oxygen,
red; carbon, grey). (b) View of the crystal packing along a axis. (c) and (d) different views of the
coordination environment of the DyIII atom.
Similar coordination modes are observed, as well as similar intradimer Dy-Dy
distances (4.05(2) Å, see Table S5 for distances and angles), and similar coordination
polyhedron (square antiprism). CSM factor is only slightly lower (CSM = 0.345)
indicating an even more symmetric D4d environment in 2 (Table S6). Overall the only
noticeable difference is the shortest interdimer Dy-Dy distance that is smaller on 2 (Dy-
Dy = 9.08(7) Å).
TGA/DSC analyses (Figure S2) clearly demonstrate that both complexes are
stable to at least 200°C and have very good sublimation properties (90% brutal weight
loss) that make them suitable for surface deposition. This is a very similar behavior to
the one of DyPyNO that has permitted its controlled deposition on surfaces. [15, 18]
4.2. Magnetic measurements
Static and dynamic magnetic susceptibility measurements were performed on
polycrystalline samples of 1 and 2 embedded in grease. The room temperature values
of the χMT products are 26.38 and 27.23 emu.K.mol-1 at 300 K, for 1 and 2,
respectively. This is slightly lower than the expected 28.34 emu.K.mol-1 for two isolated
8

DyIII ions.[38] The curves decrease as the temperature is lowered because of the
progressive depopulation of the mJ levels of the J = 15/2 multiplet of the DyIII [38]
and/or because of intramolecular Dy-Dy antiferromagnetic interaction as highlighted
on related compounds (Figure S3). [14-18, 39, 40]
Ab-initio calculations confirm these findings. In the frame of the effective spin S
= 1/2, antiferromagnetic Dy-Dy coupling is found to be Jtotal = -2.65 cm-1 and -2.99 cm-1
for 1 and 2, respectively. These values are obtained by considering the relative angles
and distances between the molecular anisotropy axes as shown on Figure 3 (dipolar
contribution, Jdip) [41] and the magnetic interaction computed (exchange contribution,
Jexch).[17] For 1 values decompose as Jtotal = Jdip + Jexch = -2.52 - 0.125 cm-1 and for 2, Jtotal
= Jdip + Jexch = -2.49 - 0.50 cm-1. These values as well as the orientation of the easy
magnetic axes are close to what obtained on DyPyNO (Jtotal = Jdip + Jexch = -2.44 - 0.25 = -
2.69 cm-1) and similar dimers. [14, 17, 42-45]
Figure 3. Representation of the easy magnetic axes on various orientation of 1 (left) and 2 (right).
9

Dynamic magnetic behavior was investigated from 1.8 K to 14 K in the 0.1-1500 Hz
frequency range in the absence of external field. Strong frequency dependence of the
in-phase (χM’) and out-of-phase (χM”) component of the magnetization is observed
(Figures 4-5, S4-S5).
The relaxation times τ were extracted by fitting χM” vs frequency curves (values
in Tables S7-S8) using an extended Debye model. The Arrhenius plot (ln(τ) vs T-1) is
reported in Figure 6. Two main regimes can be evidenced. A thermally activated
relaxation (Orbach-like relaxation, with τ = τ0exp(-Δ/kT)), above 10K and a
temperature-independent one (quantum tunneling-like relaxation with τ = τtunneling
)
below 2K. Any attempts to consider other relaxation modes failed as over-
parametrization occurs. [46] It is worth noting that on DyPyNO pure Orbach relaxation
was found only above 15K using very high frequencies (10-70kHz). In this study, we use
a conventional ac susceptometer and we were not able to isolate such a pure
relaxation regime. However it can be clearly seen from Figure 6 that the thio-
substitution (compounds 1 and 2) of the bare dimer (DyPyNO) does not damage the
energy barrier for spin reversal at high temperature. At low temperature, the
temperature-independent regime is affected and τtunneling = 0.07 and 0.04s are
observed on 1 and 2, respectively (0.38s on DyPyNO).
10

Figure 4. Temperature dependence of the out-of-phase component of the magnetization measured in
absence of external static field on 1 (top) and 2 (bottom) for frequencies ranging from 1 to 1500 Hz
(form red to blue).
The distribution of the relaxation times τ can be extracted from the Cole-Cole plots of
the in-phase and out-of phase components of the magnetization that were normalized
over the isothermal susceptibility (χT) (Figure S6 and Tables S9-S10). This allows
estimating α, considering that α = 0 for a single relaxation time (perfect SMM) up to α
= 1 for an infinity of relaxation times (spin glass). The highest α values are 0.23 and
0.27 for 1 and 2, respectively, suggesting a relatively narrow distribution of the
relaxation times. The relaxing fractions are 91% and 97% for 1 and 2. In the high
temperature region (T = 10K), α is as low as 0.15 and 0.08 for 1 and 2. This confirms
that the dimers tend to adopt an almost pure relaxation process in this temperature
region. Relaxing fractions are still very good (90% and 80% for 1 and 2).
Overall, we recall that on a structural point of view the only significant
differences between the two derivatives are a weak intermolecular Dy-Dy distance
11

change (9.08(7) Å in 2 and 11.17(9) Å in 1) and slight symmetry change of the
environment of the DyIII ion (CSM = 0.345 for 2 and 0.618 for 1). On the static magnetic
point of view the Dy-Dy distance change is too weak to induce any sizeable variation in
the total exchange value, Jtotal, via its dipolar component, Jdip.
Figure 5. Frequency dependence of the out-of-phase component of the magnetization measured in
absence of external static field on 1 (top) and 2 (bottom) for temperatures ranging from 1.8 to 14K (blue
to red).
Only weak change is seen on the low temperature relaxation time that diminish
as the coordination environment of the DyIII get more symmetric when passing from 1
to 2.
This counter-intuitive conclusion is however in agreement with recent findings that
highlight that the coordination symmetry around a given lanthanide ion is not the main
factor that governs its relaxation. Indeed both electrostatic contribution [22, 47-49]
12

(especially its quadrupolar expansion) and spin-phonon coupling are much more
relevant in tailoring the magnetic behavior of lanthanide-based SMM. [50]
Consequently, one can say that the two different thio-substitutions on the pyridine
ligand modify, but in a reasonable way, the magnetic features of the original dimer
DyPyNO. The low temperature τtunneling is slightly diminished but high temperature
energy barrier seems to be preserved in the investigated frequency range. This offers
the possibility to test both derivatives for surface deposition with a reasonable
success. Consequently we are confident that 1 and 2 could be suitable derivatives for
surface grafting.
Figure 6. Representation of the relaxation times measured on 1 (squares) and 2 (triangles) and
comparison with the already reported compound DyPyNO (circles).[12]
Conclusions
In conclusion we report here, two derivatives (1 and 2) of a well-known SMM,
(DyPyNO), targeted to be deposited on gold surfaces. The substitution of the pyridine
ring by the anchoring groups fulfills our objectives and very slightly modifies dimer’s
SMM properties. Almost no differences were found in the two substitutions; this
highlights the magnetic robustness of the DyIII core of these dimers. Indeed, given the
different geometries of the anchoring groups in 1 and 2 it would be interesting to
13

investigate their surface deposition ability on gold. We are currently testing these
possibilities.
Conflicts of interest
There are no conflicts to declare.
Acknowledgments
We acknowledge financial support from INSA Rennes, CNRS, Université de Rennes 1,
Region Bretagne, Rennes Métropole, China Scholarship Council (CSC) and the Agence
Nationale de la Recherche (ANR-13-BS07-0022-01). Thierry Guizouarn and Thierry
Roisnel are acknowledged for their assistance on magnetic and single-crystal
diffraction measurements, respectively. K.B. acknowledges Institut Universitaire de
France (IUF). B. L. G. thanks the GENCI/IDRIS-CINES Centre in France for high-
performance computing resources.
Supplementary information
Additional structural and magnetic data can be found in supplementary material.
CCDC 1819460 and CCDC 1819461 contains the supplementary crystallographic data
for 1 and 2, respectively. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html,
or
from
the
Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk.
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Anchorable derivatives of the well-known Single-Molecule Magnets (SMMs) DyPyNO are
reported. The SMM behaviors of these derivatives are remarkably well-preserved upon the
thio-substitution and offers good possibilities to graft these SMMs on surface.
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