Mixed Valence Polyoxometalates.

POMs in Molecular
Spintronics.

With the aim of the nano-fabrication of single-molecular devices, the

manipulation of the spin state of a molecule has become a challenging task in
molecular spintronics. One option to control the spin state of a molecule is that
of using electric fields or currents in order to achieve an all-electrical control of
the nanodevice.1 In fact, the use of an electric field, instead of a magnetic field,
present some advantages as it is easy to obtain (with gates or STM-tips), it
undergoes fast switching (≈ ps) and can be applied on the nanoscale, thus
providing the possibility to address selectively a single molecule. Still, very few
magnetic molecules have been proposed for this purpose, with none of these
proposals having been experimentally demonstrated. These electrically
responsive magnetic molecules are the following: 1) Spin-cossover metal
complexes, 2 2) Valence-tautomeric metal complexes,3 3) Mixed-valence metal
complexes4,5,6,7 and 4) Dipolar metal complexes, as for example asymmetric
dimers8 or molecular triangles formed by three antiferromagnetically coupled
spins.9 Notice that the most relevant examples for classes 3 and 4 are provided
by POM chemistry. In fact, Mixed Valence (MV) POMs may be ideal magnetic
molecules to study the electrical control of the spin state.
To prepare these compounds one takes advantage of the electron acceptor
ability of these metal-oxide clusters, by which a variable number of electrons
can undergo a rapid electron transfer from one centre to the other of the POM
framework. This feature shows that POMs provide unique examples in
coordination chemistry of high-nuclearity MV clusters. These spin-delocalized
clusters represent a formidable challenge in molecular magnetism since their
electronic complexity is much higher than that encountered in the spin-
localized magnetic clusters. In fact, apart form the magnetic superexchange J,
three additional processes need to be taken into account to model their
properties, namely:
• Electron transfer, t, between adjacent "occupied" and "empty" sites, i.e.
between two metals with different oxidation states (W(V)-W(VI); Mo(V)-
Mo(VI); V(IV)-V(V)), which tends to delocalize the electron over the cluster.

1 Sanvito, S. Chem. Soc. Rev. 2011, 40, 3336–3355.

2 Prins, F.; Monrabal-Capilla, M.; Osorio, E. A.; Coronado, E.; Van Der Zant, H. S. J. Adv. Mater.
2011, 23, 1545–1549.
3 Droghetti, A.; Sanvito, S.; Phys. Rev. Lett. 2011, 107, 047201.
4 Palii, A. ; Tsukerblat, B.; Clemente-Juan, J. M.; Coronado, E. J. Phys. Chem. C 2012, 116, 4999.
5 Bosch-Serrano, C.; Clemente-Juan, J. M.; Coronado, E.; Gaita-Ariño, A.; Palii, A.; Tsukerblat, B.;

ChemPhysChem, DOI: 10.1002/cphc.201200383.

6 Lehmann, J.; Gaita-Ariño, A.; Coronado E.; Loss D. Nat. Nanotech., 2007, 2, 312
7 Lehmann, J.; Gaita-Ariño, A.; Coronado E.; Loss D. J. Mater. Chem., 2009, 19, 1672.
8 Baadji, N.; Piacenza, M.; Tugsuz, T.; Della Sala, F.; Maruccio, G.; Sanvito, S. Nature Materials

2009, 8, 813.
9 Trif, M.; Troiani, F.; Stepanenko, D.; Loss, D. Phys. Rev. Lett. 2008, 101, 217201.
• Coulombic repulsion, V, between every pair of electrons, which tends to place
the electrons as far as possible to minimize its repulsion.
• Vibronic coupling, λ, that couples the “blue” electrons with the vibrational
modes of the cluster, tending to localize the electron on a given site.
In addition, the unique ability of POMs to act as electron sponges hosting a
variable number of electrons in the POM framework can provide an efficient
way to tune the strength of the exchange coupling as well as the electron
delocalization in the cluster and, consequently, its spin state. Such a control can
be achieved either physically, by an electrical gating in a single-molecule setup,
or chemically, during the synthesis of the POM.10 As we will see later on, this
feature will be quite interesting in spintronics as it is expected to afford the
control of the spin state of the cluster by applying an electric field.

Previous Work in Mixed-valence POMs as models.

In our group, one classic example of a diamagnetic MV POM was studied. This
was the anion [PW12O40]5-, which is reduced by two electrons. The
diamagnetism of this Keggin heteropolyblue was originally attributed to a
multiroute superexchange mechanism. Later on it was demonstrated that the
large spin-triplet gap could originate from the interplay between Coulombic
repulsion and electron transfer, provided the transfer routes have a certain
relation in sign and magnitude.11,12 Indeed, while the electrons are far away
from each other at all times in the ground state, the possible electron transfer
routes are different for singlets and triplets, and the result is a strong
stabilization of the singlet.
This study of the electron pair delocalization was also performed on similar
systems such as Dawson-Wells [P2W18O62]8- polyanion. In this system the
movement of electrons is focused on the two central 6 member rings. The
singlet ground state stabilization was obtained for the same signs of the single-
transfer parameters (if double-transfer processes are negligible) as in the case of
Keggin anion, and the delocalization of the electron pair implies that an
electron is delocalized over each 6-membered ring to minimize Coulomb
repulsion.13
The same behaviour was found for the decawolframate structure [W10O36]6-. 14
This polyoxometalate is a dirreduced compound where one can expect both
electrons to be localized as far as possible from each other and completely
independent. This assumption can be questioned as the system behaves as a
diamagnet. The calculation showed that the extra electrons are delocalized over
the eight equatorial wolfram sites interacting antiferromagnetically. This

10 Botar, B. ; Ellern, A.; Hermann, R.; Kögerler, P. Angew. Chem. Int. Ed., 2009, 48, 9080.
11 Borrás-Almenar, J.J.; Clemente, J.M.; Coronado, E.; Tsukerblat, B.S. Chem. Phys., 1995, 195, 1.
12 Suaud, N.; Gaita-Ariño, A.; Clemente-Juan, J.M.; Coronado, E. Chem. Eur. J., 2004, 10, 4041.
13 Borrás-Almenar, J.J.; Clemente, J.M.; Coronado, E.; Tsukerblat, B.S. Chem. Phys., 1995, 195, 16.
14 Clemente Juan, J. M.; Coronado, E.; Gaita-Ariño, A.; Suaud, N. Journal of Physical Chemistry

2007, 111, 9969–9977.

delocalization is preferred in front of having the electrons slightly far from each
other. To continue with the understanding of this phenomena another two
electron reduced POM will be presented in this thesis. In contrast with the
previously obtained behaviour, the molecule [GeV14O40]8- has a paramagnetic
ground state. A first explanation for this difference is the difference between the
aplical-equatorial distances in both systems ([W10O36]6-and [GeV14O40]8-).
Due to chemically control of electron population, polyoxovanadates represent a
remarkable class of high-nuclearity MV clusters. These compounds are
therefore ideal systems for studying the influence of the number of delocalized
electrons in the magnetic properties. [V18O48]n- cluster (Figure 4) forms a family
of compound from 18 electrons fully localize member for n=12 to mixed-
valence member with 10 delocalized electrons for n=4. 15 This series of
polyoxovanadates presents an unexpected magnetic behaviour: as the
electronic population is decreased, meaning a growing distance between
unpaired electrons, an increasing antiferromagnetic (AF) coupling is measured.
At first sight this was the opposite of what was expected. To understand it a
complete study of the influence of the exchange and transfer parameters on the
low-lying spin levels was performed. In this case, the previously explained
combination of ab initio calculations with model t-J Hamiltonian was used to
analyse the properties of this family. Unfortunately, the complete model for 10
electrons delocalized over the 18 vanadium atoms was very complex and time
expensive to calculate. Then, the authors decide to use a simplified 10 centres 6
electrons model, which successfully explained the properties showed by the
real complete system.
The main conclusion extracted was that the electron-transfer integral, calculated
from the ab initio calculations, plays the key role in the macroscopic AF
properties of these MV polyoxovanadates, while both the structural effect of
removing electrons from the initial spin-localized cluster on the amplitude of
the magnetic coupling and the effect of alleviating the spin frustration only play
a minor role.16 This was completely in agreement with the previous studies in
the cases of Keggin, Dawson and W10O366-.

15 Müller, A.; Sessoli, R.; Krickemeyer, E.; Bögge, H.; Meyer, J.; Gatteschi, D.; Pardi, L.;

Westphal, J.; Hovemeier, K.; Rohlfing, R.; Döring, J.; Hellweg, F.; Beugholt, C.; Schmidtmann,
M. Inorg. Chem. 1997, 36, 5239.
16 Calzado, C.J.; Clemente-Juan, J. M.; Coronado, E.; Gaita-Ariño, A.; Suaud, N. Inorg. Chem.,
2008, 47, 5889.
Figure 3. a) Structure of [V18O48]n- cluster and b) temperature dependence of χT for the spin-
localized n=12 and delocalized n=4

In addition to the previous studies, the effect of vibronic coupling on electron

location was studied for the two electron reduced Keggin anion taking into
account an adiabatic approximation. 17 The conditions of singlet and triplet
stabilization discussed above are strongly affected by the vibronic interactions
that tend to localize the electrons and thus effectively reduce the transfer
parameters. The degrees of localization are proved to be different for the spin-
triplet and spin-singlet states that essentially influence the magnetic properties
of the reduced Keggin anion. For a strong vibronic coupling, spin-triplet states
becomes partial or even full localized, and full delocalized states can be
achieved only for spin-singlets. For weak vibronic coupling in all case a full
delocalized configuration can be found. The adiabatic approximation gives very
qualitative information about localization and restricts the accuracy of
calculations of the magnetic characteristics and profiles of the intervalence
optical bands. Recently it has been presented a powerful theoretical approach to
obtain an accurate solution of the dynamic vibronic problem in large scale Jahn-
Teller (JT) systems. The approach uses a symmetry adapted vibronic basis to
reduce the dimension of the problem.18 The application of this procedure to
Keggin anion is being developed place and hope to give accurate description of
combined JT/ pseudo JT problems for the spin-singlet and spin-triplet states in
the high-nuclearity system..

In conclusion, POMs are model systems to study the interplay between electron
delocalization and magnetic exchange in high-nuclearity clusters. Their highly
symmetric structures facilitate the development of exact quantum-mechanical
models from which a clear picture of the local parameters involver in the
magnetic properties can be extracted.

Borrás-Almenar, J.J.; Clemente, J.M.; Coronado, E.; Tsukerblat, B.S. Chem. Phys., 1995, 195, 29.
17

Tsukerblat, B.; Palii, A.; Clemente-Juan, J. M.; Gaita-Ariño, A.; Coronado, E. Int. J. Quantum
18

Chem., 2012, DOI: 10.1002/qua.24152

Aim of the Work.

Molecular spintronics was a new-born field when this thesis started. The
previous examples presented and studied in our group were a successful
demonstration of the ability of the theoretical models to predict and explain the
behaviour of very complex mixed-valence systems. Most of these examples
were based on polyoxometalate structures which are the main compounds
studied in this thesis.

In this way, we focused on the synthesis and theoretical study of new MV-POM
complexes and their possibly application in spintronics. To achieve this goal, a
computational code called MVPACK was developed and improved including
not only delocalized electrons but also the explicit effect of an external electric
field perturbation. In the synthetic part, a new compound with formula
[PMoVI11MoVO40{Ni(phen)2(H2O)}2], has been developed. This compound,
together with the previous showed [GeV14O40]8- anion, were theoretically
studied and their behaviour explained and justified.

EMPIEZA LA EXPLICACIÓN DEL TRABAJO HECHO POR MI.

MIXED VALENCE – EFFECTIVE HAMILTONIAN CODE.

Theoretical background

To study the mixed valence systems we used two different theoretical

approximations.
Ab initio + Effective Hamiltonian
In the first one a combination of ab initio calculations with model t-J
Hamiltonian was usually used. 19 This method consists in a obtaining the
magnetic energy levels using a wave-function calculation (typically CASSCF-
CASPT2). Due to the complexity in the total molecule calculation we only
consider a pair of metals and its first coordination sphere on each attempt. The
rest of the molecule is only considered as punctual charges with
pseudopotentials on its original atom positions. This procedure is called
“embedded fragment method”. The next step is to obtain effective parameters
(t, J, V and ε) using an effective Hamiltonian (applied to only that dimer) that
considers only the electronic part as follows:
  1
Η = ∑ ε i ⋅ ni + ∑ tij ∑ (ci†σ c jσ + c†jσ ciσ ) − ∑ J ij (Si ⋅ S j − ni n j ) + ∑ Vij ⋅ ni n j
i i, j σ i, j 4 i, j

The ab initio parameters obtained from the dimer calculation are introduced as
an input to compute a total molecular structural description. Then, the code
calculates the energy matrix and diagonalizes it to obtain the eigenvalues and
the thermodynamic properties such as the magnetic behaviour. Using this
approach, it is possible to study very large systems maintaining a very accurate

Suaud, N.; Gaita-Ariño, A.; Clemente Juan, J. M.; Sánchez-Marín, J.; Coronado, E. Journal of the
19

American Chemical Society 2002, 124, 15134–15140.

description of the electronic/magnetic behaviour. In fact in our group a
computational code has been developed to calculate mixed-valence systems
using this method.20
Here we present a brief survey of how is this effective Hamiltonian approach
adapted to the general case of magnetic MV compounds. The definition of the
system considers N metal sites and arbitrary number P of delocalized electrons
as schematically shown in Fig. 1.

For the sake of simplicity we will usually ignore the case of a strong one-site
Coulomb repulsion, so that the configurations with two (or more) electrons on
the same site are excluded. In this sense we imply the restriction P < N that can
be removed in the framework of the developed procedure provided that a more
sophisticated consideration is required. We assume also that under certain
reasonable physical conditions the whole system can be divided into K mixed-
valence domains each one containing Nr (r = 1, 2, …K) metal sites (N1+ N2+…
NK = N). Each domain contains arbitrary number Pr of delocalized electrons
(P1+ P2+… PK = P), so that the domains are represented by the mixed-valence
nr +1 nr +1
+ (N r − Pr ) d
nr
clusters of the type of Pr d containing Pr ions in d
n
configuration and [Nr - Pr] ions in the d r configuration. Electron transfer
processes are assumed to be possible only between the centres of each domain.

In general, the localized domains can be heteronuclear, that is, they can contain
different ions (spins). The systems containing both localized and delocalized
domains can be termed as mixed valence systems with partial electron
delocalization (examples of such kinds of systems are the polyoxovanadates
clusters). 21

For some of the calculations later presented the influence of an external electric
field is introduced. That was done by taking into accounts that its main effect is
to modify the orbital energy of the metal centers depending on its position
along the direction of the field. In fact, an orbital is stabilized compared to

another one when it is in a higher electric potential. In an electric field E , the

20Borrás-Almenar, J. J.; Cardona-Serra, S.; Clemente Juan, J. M.; Coronado, E.; Palii, A. V.;
Tsukerblat, B. S. J. Comput. Chem. 2010, 31, 1321–1332.
21 A) Gatteschi, D.; Tsukerblat, B. S. Chem Phys 1996, 202, 25-37. B) Gatteschi, D.; Tsukerblat, B.

S.; Barra, A. L.; Brunel, L. C.; Müller, A.; Doring, J. Inorg Chem 1993, 32, 2114-2117. C)
Gatteschi, D.; Tsukerblat, B. S. Mol Phys, 1993, 79, 121-143.
orbital energies ε are then assumed to be modified according to the following
equation:
 
ε i − ε j = (ε i0 − ε 0j ) + E i rij

where rij is the vector between centers i and j and ε i0 and ε 0j are the orbital
energies of sites i and j in absence of electric field.

DFT

The second approach used in this thesis is to compute the complete molecule by
the means of a Density Functional method.

A Density functional theory (DFT) calculation is a quantum mechanical method

used in physics and chemistry to investigate the electronic structure of a many-
body system. With this theory, the properties of a many-electron system can be
determined by using functionals (functions of another function), which in this
case is the electronic density.
DFT has been very popular for calculations in solid-state physics since the
1970s. However, DFT was not considered accurate enough for calculations in
quantum molecular chemistry until the 1990s, when the approximations used in
the theory were improved to model the exchange and correlation interactions.
In many cases the results of DFT calculations for solid-state and molecular
systems agree quite satisfactorily with experimental data. Computational costs
are relatively low when compared to traditional ab initio methods, such as
previously presented Hartree–Fock theory and its descendants based on the
complex many-electron wavefunction.
There are some advantages of this technique over the previous one. One
obvious improvement is that the calculation includes the complete molecule
(and its surroundings if necessary). This can be important because considering
the outer electron core of every atom at the same time can give some insight
about effects such as polarization by an external electric field. This property
was not explicitly considered in the previous method and we demonstrated to
be crucial to take it into account in some specific calculations. Other advantage
is the possibility to introduce the effect of an external electric field that can be
oriented at will and to compute the effect of this perturbation over the whole
electronic structure of the molecule.

But DFT has also some disadvantages in front of wave-function methods. The
functional is usually chosen just trusting other calculations where it has been
successfully used to explain the properties. There is not a clear way to improve
the calculation other than increasing the basis set size or using other functional,
which is not always a correct path. This is what makes the property prediction a
difficult task for DFT methods.

In this thesis all the DFT calculations have been carried out using the
GAUSSIAN03 22 code within the same hybrid functional B3LYP. 23 This has

22 GAUSSIAN 03 – Gaussian Inc.; Pittsburg, PA, 1998.

been for long, the most used functional in theoretical magnetochemistry. Many
authors use this functional as one of the most accurated approaches to
understand the spin interaction.24 By the means of the electronic atomic basis,
our calculations have been performed at CREMBL basis set.25

ARREGLAR HASTA AQUI!

POMS APLICACIONES SPINTRÓNICA.

This section is dedicated to the previous work in MV POMs that have been
interesting to molecular spintronics. The possibility of change their ground spin
state by the application of an external electric field, or electric injection of extra
electrons make them promising candidates to achieve the goal of this discipline.
The basis for having a magnetic switching, is to stabilize two levels with
different electronic properties, which are close enough in energy to overcome
this difference by applying an electric stimulus.
One possibility studied by our group was provided by [PMo12O40(VO)2]q-
(Figure 1). In this POM two (VO)2+ are sitting at opposite tetragonal sites of the
Keggin anion and host a S=1/2. On the other hand, the central Keggin structure
PMo12O40 can act as electron acceptor giving rise to a MV cluster able to
accommodate a variable number of electrons. Thus, when the number of
injected electrons is odd, the delocalized spin of the central Keggin cluster will
be strongly coupled with the two localized spins located at the (VO)2+. As a
result, these two distant spins will be ferromagnetically coupled. In turn, if the
number of injected electrons is even, the coupling between the localized spins
will be very weak. The injection of electrons can be performed through the
tunneling current provided by a STM setup. Hence, in this device a control of
the exchange interaction through injection of electrons can be achieved. The use
of this kind of device as an electrically addressable quantum gate will be
discussed in the next section.
Other example of switchable magnetic POM is provided by the bicapped
mixed-valence polyoxometalate, [PMoVI11MoVO40{Ni(phen)2(H2O)}2], where two
Ni2+ (S=1) are placed in two opposite MoO6 positions. In this case, a compound
with an odd number of delocalized electrons has been isolated, and, as
expected, the “extra” electron, which is fully delocalized at room temperature,
is simultaneously coupled antiferromagnetically with the two S=1 sites. The
result is an effective S=3/2 ground state (two parallel spins S = 1
antiferromagnetically coupled to a central spin S = ½). At temperatures around
10 K, a trapping of this central spin nearby one Ni2+ center occurs as a
consequence of the vibronic coupling. As a consequence, the magnetic
communication between the Ni2+ centers is effectively switched off so as the
ground state corresponds to that of two independent spins: an S=1/2, coming

23 Becke, A. D.; J. Chem. Phys. 1993, 98, 5648-5652.

24 Cremades, E.; Cauchy, T.; Cano, J.; Ruiz, E. Dalton Trans. 2009, 5873.
25 Pacios L.F.; Christiansen, P. A.; J. Chem. Phys. 1985, 82, 2664-2671.; Hurley M.M.; Pacios L.F.;

Christiansen, P. A.; Ross, R. B.; Ermler, W. C. J. Chem. Phys. 1986, 84, 6840-6853.
from the antiferromagnetic coupling between the S=1 and the trapped spin S =
½, and an S=1 from the second Ni2+ center.26 In this case the switch between the
different spin states is thermally controlled.

Figure 1. Structure of [PMo12O40(VO)2]q- and [PMoVI11MoVO40{Ni(phen)2(H2O)}2] anions.

The last POM complex discussed in this thesis is the mixed-valence

K2Na6[GeV14O40] molecule. This compound is obtained as a dirreduced anion
with two “extra” electrons. It contains 12 spin-less VV ions and 2 S=1/2 VIV ions.
The unique feature of this POM is that it is paramagnetic. This behavior is in
sharp contrast with what has been typically observed in other 2e-reduced
POMs, which are diamagnetic at room temperature since the two “extra”
electrons are strongly antiferromagnetically coupled.27

26
Cardona-Serra, S.; Clemente-Juan, J.M.; Coronado, E.; Gaita-Ariño, A.; Martí-Gastaldo, C.;
(unpublished results)
27 Kozik, M.; Hammer, C. F.; Baker, L. C. W. J. Am. Chem. Soc. 1986, 108, 2748-2749. Kozik, M.;
Baker, L. C. W. J. Am. Chem. Soc. 1987, 109, 3159-3160. Kozik, M.; Casañ-Pastor, N.; Hammer, C.
F.; Baker, L. C. W. J. Am. Chem. Soc. 1988, 110, 7697-7701. Kozik, M.; Baker, L. C. W. J. Am. Chem.
Soc. 1990, 112, 7604-7611. Casañ-Pastor, N.; Baker, L. C. W. J. Am. Chem. Soc. 1992, 114, 10384-
10394.