Experimental and Theoretical Identification of the Origin of Magnetic Anisotropy in Intermediate Spin Iron(III) Complexes

Article abstract of DOI:10.1002/chem.201705989

The complexes [FeL^N2S2X] [in which L^N2S2=2,2′-(2,2′-bipryridine-6,6′-diyl)bis(1,1′-diphenylethanethiolate) and X=Cl, Br and I], characterized crystallographically earlier and here (Fe(L)Br), reveal a square pyramidal coordinated Fe^III ion. Unusually, all three complexes have intermediate spin ground states. Susceptibility measurements, powder cw X- and Q-band EPR spectra, and zero-field powder M?ssbauer spectra show that all complexes display distinct magnetic anisotropy, which has been rationalized by DFT calculations.

Full text of DOI:10.1002/chem.201705989

A Journal of
Accepted Article
Title: Experimental and Theoretical Identification of the Origin of
Magnetic Anisotropy in Intermediate Spin Ground State Iron(III)
Complexes.
Authors: Lianke Wang, Matija Zlatar, Filip Vlahovic, Serhiy Demeshko,
Christian Philouze, Florian Molton, Franc Meyer, Carole
Duboc, Maja Gruden, and Marcello Gennari
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To be cited as: Chem. Eur. J. 10.1002/chem.201705989
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Supported by

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Experimental and Theoretical Identification of the Origin of
Magnetic Anisotropy in Intermediate Spin Iron(III) Complexes.
Lianke Wang,[a] Matija Zlatar,[b] Filip Vlahović,[c] Serhiy Demeshko,[d] Christian Philouze,[a] Florian
Molton,[a] Marcello Gennari,[a] Franc Meyer,[d] Carole Duboc*[a] and Maja Gruden*[c]
Abstract: The complexes [FeLN2S2X] (where LN2S2 = 2,2’-(2,2’-
in Fe(L)I) with the halide occupying the apical position and the
N2S2 donor atoms of LN2S2 constituting the equatorial plane. All
bipryridine-6,6’-diyl)bis(1,1’-diphenylethanethiolate) and X = Cl, Br
and I), characterized crystallographically earlier and here (Fe(L)Br),
reveal a square pyramidal coordinated FeIII ion. Unusually, all three
complexes have intermediate spin ground states. Susceptibility
measurements, powder cw X- and Q-band EPR spectra, and zero-
field powder Mössbauer spectra show that all complexes display
distinct magnetic anisotropy, which has been rationalized by DFT
calculations.
Fe-N/S distances and valence angles are similar, however an
expected difference arises from the Fe-X distances (2.313 Å in
Fe(L)Cl, 2.473 Å in Fe(L)Br and 2.673 Å in Fe(L)I) in agreement
with the different ionic radii of the halides (see S1). This is
compensated by a variation of the position of the iron ion with
respect to the mean equatorial plane formed by the N2S2
atoms. The iron ion resides 0.537, 0.512 and 0.476 Å out of this
plane towards the axial chlorido, bromide and iodido ligands,
respectively. The long Fe…Fe distances observed in each
crystal demonstrate that the three mononuclear FeIII complexes
are magnetically isolated species (the shortest Fe…Fe distance:
8.965, 8.868 and 8.958 Å, in Fe(L)X, X = Cl, Br, I, respectively).
Predicting and rationalizing the electronic and magnetic
properties of transition metal ions is a core challenge in
coordination chemistry. This is particularly important for
complexes that exhibit non-standard ground states, such as
intermediate spin systems. The latter are relatively uncommon
but critically important in, for example, the study of spin-cross-
over processes, single ion single-molecule magnets, and in
(enzymatic) catalysis.[1] In the case of FeIII (d5), intermediate spin
ground states are observed mainly for complexes of square
pyramidal coordination geometry with few exceptions found in
octahedral or square planar complexes in case of suitable ligand
environments.[2] Although the electronic and magnetic properties
of a number of mononuclear S = 3/2 FeIII complexes have been
the subject of detailed experimental studies, the corresponding
computational studies are limited to the determination of the spin
of their ground states, and, to the best of our knowledge, the
present report is the first theoretical consideration of the origin of
their magnetic anisotropy.[1a, 1d, 3]
Scheme 1. Synthesis of Fe(L)X (X=Cl, Br, I)
The temperature dependence of the T product for Fe(L)Br and
Fe(L)I is shown in Figure 1 together with that of Fe(L)Cl for
comparison. The room temperature T values for all complexes
are consistent with the expected values for S = 3/2 species. This
is also confirmed by Density Functional Theory (DFT)
calculations performed at OPBE[6] and S12g[7]/TZ2P level of
theory, which was shown to be accurate for spin state
energetics.[8] Separate optimizations for the three possible spin
states (low, intermediate, high) reported in Table 1 show clearly
that the intermediate-spin state, S=3/2, is in all cases the spin
ground state, whereas the order of excited states depends on
the level of theory (Table S3.1). The geometries of optimized
S=3/2 complexes are in excellent agreement with X-ray
structures, with an r.m.s. error of less than 1.3 pm (Table S3.2,
Figure S3.1).
Here we report a series of closely related mononuclear square
pyramidal FeIII complexes that display an intermediate spin
ground state, and we take advantage of this unique opportunity
to carry out combined experimental and theoretical studies that
are essential to develop a rational correlation between their
structural and magnetic properties.
The [FeLN2S2X] complexes (with LN2S2 = 2,2’-(2,2’-bipyridine-6,6’-
diyl)bis(1,1’-diphenylethanethiolate) and X = Cl, Br and I),
Fe(L)Cl, Fe(L)Br and Fe(L)I, were isolated following the reaction
of LN2S2 with FeX3 (X = Cl[4] and Br) in tetrahydrofuran (THF) or
between the dinuclear FeII disulfide complex FeII SS[5] and an
2
excess of tetra-n-butylammonium iodide in acetonitrile (MeCN)
for Fe(L)I (Scheme 1). The structures of Fe(L)Br and Fe(L)I is
reported in Figure S1.1, while the structure of Fe(L)Cl[4] was
reported earlier. All three complexes are obtained with a penta-
coordinated iron center in a distorted square pyramidal geometry
(τ5 value of 0.328 in Fe(L)Cl, 0.317 in Fe(L)Br and 0.291
Table 1. Spin state energetics (kcal/mol-1) of Fe(L)X (X=Cl, Br, I) relative to
intermediate spin ground state calculated using two different levels of theory
S
Fe(L)Cl
7.7
Fe(L)Br
7.4
Fe(L)I
6.4
LS* (**)
IS*
1/2
3/2
5/2
1/2
3/2
5/2
[a]
Lianke Wang, Dr. Christian Philouze, Florian Molton and
Dr. Carole Duboc*
University of Grenoble Alpes, DCM,
CNRS UMR 5250,
Grenoble, France
E-mail: carole.duboc@univ-grenoble-alpes.fr
Dr. Matija Zlatar
Institute of Chemistry, Technology and Metallurgy
University of Belgrade
Filip Vlahović and Prof. Maja Gruden*
Faculty of Chemistry
OPBE/TZ2P
S12g/TZ2P
0.0
0.0
0.0
HS*
5.5
6.3
7.5
LS* (**)
IS*
7.8
7.7
6.2
[b]
[c]
0.0
0.0
0.0
HS*
5.3
6.1
7.0
*LS- low spin, IS- intermediate spin, HS- high spin
** Spin projection technique (both for the energy and the gradients) to correct
the spin contamination has been used.
University of Belgrade
Studentski trg 12–16, 11000 Belgrade, Serbia
E-mail: gmaja@chem.bg.ac.rs
Dr. Serhiy Demeshko and Prof. Franc Meyer
Universität Göttingen
[d]
Institut für Anorganische Chemie
Tammannstr. 4, D-37077 Göttingen, Germany
Supporting information for this article is given via a link at the end of
the document
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The intermediate spin ground state is a consequence of strong
further decomposed into four terms according to single electron
excitations: αα - from singly occupied molecular orbitals
(SOMO) to the virtual orbitals (VMOs); ββ - from doubly
occupied orbitals (DOMO) to SOMO; αβ – spin flip between
SOMOs; βα – from DOMO to VMO. The first two contributions
arise from excitations that lead to S=3/2 excited states, the third
to S=1/2 excited states, and the last to S=5/2 excited states. In
the case of Fe(L)Br, excitations to both doublet and quartet
and covalent bonding in the xy plane, and weak bonding
between the metal ion and the axial ligand. Hence, the dx2
2
-y
orbital is the highest in energy and well separated from the other
four metal-based orbitals, including the dz2 orbital. At the same
time, nephelauxetic reduction due to the covalency decreases
pairing energy, leading to the double occupation of the mainly
non-bonding dxy orbital, and thus to an S=3/2 ground state
(Figures S3.2 and S3.3).
The magnetic properties of an S=3/2 system, such as the
present Fe(L)X complexes, can be described by a Spin
Hamiltonian that includes the zero field splitting (ZFS) terms and
the electronic Zeeman interaction (Equation (1)).
states contribute to DSOC
, while for Fe(L)Cl and Fe(L)I
excitations to doublets represent the main contribution. Besides,
it should be noted that in the iodido and chlorido complexes the
first excited states differ being S = 5/2 and S = 1/2, respectively
(Table S3.1). These data can be thus related to a larger DSOC
(αβ) magnitude for Fe(L)I with respect to that of Fe(L)Cl.


1



Equation (1)
2
2
2
ˆ
ˆ
ˆ
ˆ
E
H = D Sz  S(S+1)
(Sx  Sy ) gμB B  S



D
3
with S being the spin, D and E the axial and rhombic ZFS
parameters and g the isotropic electronic Zeeman interaction.
The magnetic susceptibilities of the complexes remain constant
down to ca. 30 K. At lower temperatures, the T values
decrease, as expected for moderate ZFS. Powder cw X- and Q-
band EPR spectra recorded at low temperatures (5-30 K)
display features at low field corresponding to transitions between
the Kramers doublet MS = ± 3/2 (Figures S2.1-2). E/D values of
0.18, 0.13 and 0.12 (Table 2) were estimated for Fe(L)Cl,
Fe(L)Br and Fe(L)I, respectively, from the detailed analysis of
the spectra (S2 and Figures S2. 3-5). The E/D decrease from
Fe(L)Cl to Fe(L)I is consistent with the distortion around the Fe
center that increases concomitant with the τ5 values. The
temperature dependence of MT and variable temperature-
variable field (VTVH) magnetization data were simultaneously
fitted using these E/D values to estimate the D values, 3.7, 5.2
and 11.5 cm–1 for Fe(L)Cl, Fe(L)Br and Fe(L)I, respectively
(Table 2). The trend, i.e. an increase of D with the increase of
the halide SOC, is generally observed[9] in mononuclear 3d
complexes with only a few exceptions.[10]
Table 2. Experimentally determined spectroscopic parameters of Fe(L)Cl,
Fe(L)Br and Fe(L)I
Fe(L)Cl
Fe(L)Br
Fe(L)I
ΔΕQ (mm.s-1)
2.82
3.00
3.14
δ (mm.s-1)
D (cm-1) [a]
E/D [b]
0.46
3.7
0.44
5.2
0.42
11.5
0.12
2.08
0.18
2.10
0.13
2.05
g [a]
[a] by SQUID measurements; [b] by EPR spectroscopy.
The ZFS parameters of the three complexes were calculated in
the framework of the coupled-perturbed DFT approach (CP-
DFT)[11], (Table 3). The influence of the level of theory and
comparison with data obtained with LF-DFT[12] are provided as
Supporting Information (see S4). Experimental and calculated D
values are in a good agreement concerning both their magnitude
and sign. While predicted D values are in good agreement with
the experimental data, the calculated E/D values display
significant deviation, as often observed in a DFT framework.[13]
Generally, the main factor driving the magnetic anisotropy is the
spin−orbit coupling (SOC). Interestingly, the trend in magnetic
anisotropy is seen where D is decomposed into its SOC (DSOC
)
and spin–spin dipolar contribution (DSSC) terms using CP-DFT
(Table 3). As expected, DSOC dominates over DSSC. The
contribution of DSSC is not negligible in the case of Fe(L)Cl
(around 13% of the total D) but decreases from Fe(L)Cl to
Fe(L)I. The importance of dominant DSOC contribution increases
from the chlorido to the iodido metal complexes, explaining the
observed trend in D values. In an attempt to rationalize the origin
of the difference in DSOC between the three complexes, DSOC is
Figure 1. MT versus T plot for Fe(L)Cl (top), Fe(L)Br (middle) and Fe(L)I
(bottom). The insets show variable temperature–variable (VTVH)
magnetization measurements as Mmol versus BB/kT. Solid lines represent the
calculated curve fits (see text).
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Table 3. Calculated Mössbauer and ZFS Parameters of Fe(L)Cl, Fe(L)Br and
Fe(L)I and decomposition of D parameter into various contributions
QTW Bruker cavity. All spectra were recorded at 7K on powder samples.
Temperature-dependent magnetic susceptibility measurements were
carried out with a Quantum-Design MPMS-XL-5 SQUID magnetometer,
and Mössbauer spectra were recorded with a 57Co source in a Rh matrix
using an alternating constant-acceleration Wissel Mössbauer
spectrometer operated in the transmission mode and equipped with a
Janis closed-cycle helium cryostat; further details can be found in the SI.
Fe(L)Cl
2.74
0.43
2.34
0.17
0.26
2.08
0.33
0.45
1.70
-0.42
Fe(L)Br
2.82
0.42
4.72
0.06
0.13
4.59
0.51
2.01
1.64
0.43
Fe(L)I
ΔΕQ (mm.s-1)
δ (mm.s-1)
2.85
0.41
D (cm-1)
12.42
0.32
Synthesis of Fe(L)Br. Solid NaH (60% in mineral oil, 14 mg, 0.3 mmol)
was added to the solution of H2LN2S2 (50 mg, 0.086 mmol) in THF (2 mL)
at 293 K. After 20 min, the excess NaH was removed by filtration and a
solution of FeBr3 (28 mg, 0.095 mmol) in THF (3 mL) was added to the
yellow solution under stirring. During the addition, the color of the solution
turned to red, and subsequently to deep red. A brown-red precipitate
formed over several few minutes. The mixture was stirred for 1 h. The
precipitate was isolated and redissolved in dichloromethane and
subsequently filtered to remove residual solid. The solvent was removed
from the filtrate in vacuo and the residual solid dried and collected as a
deep red powder (39mg, 63.4%). Single crystals suitable for X-ray
diffraction analysis were obtained by slow diffusion of diethyl ether into
the solution of the product in CH2Cl2:CH3CN (4:1) at 293 K.
E/D
DSSC (cm-1)
DSOC (cm-1)
DSOC (αα) (cm-1)
DSOC (ββ) (cm-1)
DSOC (αβ) (cm-1)
DSOC (βα) (cm-1)
0.00
12.42
-0.63
-1.67
18.19
-3.47
Synthesis of Fe(L)I. Solid n-tetrabutylammonium iodide (44 mg, 0.119
mmol) was added to a suspension of the dinuclear [FeII2(LSSL)](ClO4)2
FeIISS (35 mg, 0.024 mmol) in CH3CN (10 mL). After few min, a brown
precipitate was formed. After stirring for 1h, the solid was isolated by
filtration, washed with MeCN, dried under vacuum and collected as dark
brown powder (32 mg, 0.042 mmol, 88%). X-ray suitable single crystals
of Fe(L)I were obtained by slow diffusion of diethyl ether into the solution
of the product in CH2Cl2:CH3CN (4:1) at 293 K.
Computational details. Density Functional Theory (DFT) calculations,
using Amsterdam Density Functional program package (ADF2016)[14]. In
first step geometry optimizations were performed using two general
Figure 2. Mössbauer spectra of solid samples of Fe(L)Br (left) and Fe(L)I
(right) recorded at 80 K.
gradient approximations (GGA) in the form of OPBE[15] and S12g[16]
.
Scalar relativistic corrections have been included self-consistently in all
calculations by using the zeroth-order regular approximation (ZORA)[17]
.
Zero-field powder Mössbauer spectra recorded at 80 K (Table 2,
Figure 2) show that the quadrupole splitting (ΔΕQ values) is
sensitive to the nature of the coordinating halide, with increasing
values from Fe(L)Cl to Fe(L)I. By contrast the isomer shift δ is
comparable for all complexes (0.42-0.46 mm.s-1) and in the
expected range for an intermediate spin ground state. The slight
decrease of δ upon going from Fe(L)Cl to Fe(L)I, which reflects
different s-electron density at the nucleus, is consistent with the
more covalent character of the Fe-X bond for heavier halides.
These values are corroborated by DFT calculations (Table 3).
Optimizations of all spin states for three complexes under investigation
were performed by letting the structure of each spin state relax towards
its own equilibrium geometry separately. Molecular orbitals were
expanded in an uncontracted set of Slater type orbitals (STOs) of triple-
zeta quality with two polarization function (TZ2P)[18] full electron basis
set. All calculations were done in a spin-unrestricted fashion; the very
good Becke grid was used. Calculations of ZFS were performed on the
experimentally determined X-ray structures using coupled perturbed
SOC DFT method at BP86[19] ZORA-def2-TZVP[20] level of theory, as
implemented in ORCA (version 4.0.1.2)[21]. Mössbauer parameters have
been calculated at OPBE/TZP level of theory according to the procedure
by Noodleman et al..[22] Further details are provided in S4.
In summary, the present combined experimental and theoretical
approach enables the rationalization of experimental data
leading to a more complete understanding of the electronic
structure of such systems and of the factors that govern the
contribution of the different excited spin states in the magnetic
anisotropy of intermediate spin state FeIII complexes. The origin
of the magnetic anisotropy, and even the trend in values, differs
from our earlier studies on the same ligand system with CoIII
(S=1),[10e] and different complexes with S = 3/2 (MnIV),[13c] which
is a clear indication that any change induces different magnetic
behavior depending on the spin system and analogies cannot be
drawn a priori with systems that are yet to be investigated.
Understanding of these effects and the potential for DFT
methods to predict them, opens new opportunities in the rational
design of magnetic materials with desired properties.
Acknowledgements
The following organizations are acknowledged for financial support:
the Serbian Ministry of Science (GrantꢀNo. 172035), Serbian-French
collaboration project number 451-03-39/2016-09/06 (Serbian
number) or 36224WB (French number), Labex arcane (ANR-11-
LABX-003), the Deutsche Forschungsgemeinschaft (collaborative
DFG/ANR project Me1313/14-1) and the China Scholarship Council
(PhD scholarship to Lianke Wang). This work was performed in the
framework of COST Action CM1305 ‘‘Explicit Control Over Spin-
states in Technology and Biochemistry (ECOSTBio)’’.
Keywords: intermediate spin state • iron(III) • DFT calculations •
magnetic properties • electronic structure
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10.1002/chem.201705989
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Lianke Wang, Matija Zlatar, Filip
Vlahović, Serhiy Demeshko, Christian
Philouze, Florian Molton, Marcelllo
Gennari, Franc Meyer, Carole Duboc*
and Maja Gruden*
Page No. – Page No.
Effect of halide ligands on the
magnetic anisotropy in a series of
square pyramidal Fe(III) complexes
with an S = 3/2 ground state.
Experimental and Theoretical
Identification of the Origin of
Magnetic Anisotropy in Intermediate
Spin Iron(III) Complexes.
This article is protected by copyright. All rights reserved.