Post-synthetic Modification of a Dinuclear Spin Crossover Iron(III) Complex

Article abstract of DOI:10.1002/zaac.201800087

The dinuclear iron(III) complex [Fe(salten)₂(bipytz)](BPh₄)₂·EtOH (1) was synthesized and its post-synthesis modification yielded [Fe(salten)₂(bipydz)](BPh₄)₂·EtOH (2). The crystal structures and magnetic behaviors of 1 and 2 were investigated by variable temperature XRD, magnetic susceptibility, and M?ssbauer spectra measurements, with each of these dinuclear iron(III) complexes exhibiting gradual spin crossover behavior.

Full text of DOI:10.1002/zaac.201800087

Title: Post-synthetic modification of a dinuclear spin crossover iron(III)
complex
Authors: Yuki Komatsumaru, Manabu Nakaya, Fumiya Kobayashi,
Ryo Ohtani, Masaaki Nakamura, Leonard Lindoy, and Shinya
Hayami
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To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.201800087
Link to VoR: http://dx.doi.org/10.1002/zaac.201800087

10.1002/zaac.201800087
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
Post-synthetic modification of a dinuclear spin crossover iron(III)
complex
Yuki Komatsumaru,[a] Manabu Nakaya,[a] Fumiya Kobayashi,[a] Ryo Ohtani,[a] Masaaki Nakamura,[a]
Leonard F. Lindoy[b] and Shinya Hayami*[a],[c]
Dedicated to Professor Peter Comba on the Occasion of his 65th Birthday
Abstract:
This has allowed their potential application in molecular electronic
devices.[6] Up to now, numerous SCO compounds have been
reported,[6-13] with most of these involving a hexacoordinated
iron(II), iron(III), or cobalt(II) metal environment.[7] Over the last
two decades or so, a number of MOFs exhibiting SCO behavior
have been reported as well as that of numerous mono-, di-, and
multi-nuclear SCO compounds.[8] Complete, abrupt, and
hysteretic spin conversions (also termed spin transitions (ST)) are
now all well documented.[9] However, the control of such
behaviors remains a continuing motivation for much of the
research in this area,[10,11] with the generation of abrupt or
hysteretic ST behavior being of particular interest. Ligand
modification, choice of counter ion, and/or crystalizing solvent
have all been employed to tune the nature of a given observed
ST.[11]
The dinuclear iron(III) complex [Fe(salten)2(bipytz)](BPh4)2·EtOH (1)
was synthesized and its post-synthesis modification yielded
[Fe(salten)2(bipydz)](BPh4)2·EtOH (2). The crystal structures and
magnetic behaviors of 1 and 2 were investigated by variable
temperature XRD, magnetic susceptibility and Mössbauer spectra
measurements, with each of these dinuclear iron(III) complexes
exhibiting gradual spin crossover behavior.
Introduction
John and co-workers have investigated the SCO behavior of
the MOF, [Fe(bipytz)(Au(CN)2)2] (bipytz = 3,6-bis(4-pyridyl)-
1,2,4,5-tetrazine). Their focus was on the structural stability of this
MOF and they were able to control the SCO behavior by
converting the bipytz linker to a bipydz (bipydz = 3,6-bis(4-
pyridyl)-1,2-diazine) linker by PSM.[12] The latter conversion
involved an inverse-electron-demand, retro-Diels-Alder reaction.
Since most commonly, the SCO behavior of MOFs has been
tuned by the use of guest molecules,[13] the above PSM approach
represented a new stratergy for controlling magnetic behavior.
In the present study, we have employed a discrete SCO
complex (not a MOF) also incoporating a bipytz ligand as a bridge
between Fe(III) sites; our aim was also to control SCO behavior
via structural/electronic changes produced by the PSM.
Post-synthetic modification (PSM) commonly occurs in
biochemistry. For example, it occurs in the post-translational
modification of proteins, whereby chemical functionality is
introduced by chemical modification of an intact polypeptide.[1]
Recently, PSM has been increasingly used as a synthetic
procedure for the modification of materials to produce new
products that are otherwise difficult to prepare directly.[2] In
particlar, PSM has proved to be a useful technique for the
modification of porous materials such as silica, coordination
polymers (CPs) and metal-organic-frameworks (MOFs); leading
to modified frameworks that influence their gas adsorption
properties.[3] Furthermore, PSM has been used for controlling the
physical properties of solid state materials, including their
magnetic[4] and photo-luminescence properties.[5]
The
[Fe(salten)2(bipytz)](BPh4)2·EtOH (1; H2salten
[iminobis(3,1-propanediylnitrilomethylidyne)]bis-phenol)
dinuclear
iron(III)
complex,
Spin crossover (SCO) materials exhibiting low-spin (LS) – high-
spin (HS) conversion in response to external stimuli (temperature,
light irradiation, pressure, and the presence of guest molecules)
have been widely-investigated due to their controllable spin states.
=
2,2-
was
synthesized and its SCO behavior and crystal structure (Figure
1(a)) were determined. Compound 1 exhibits gradual as well as
complete SCO behavior, with the nature of its ST also confirmed
by variable temperature X-ray structural analysis. PSM was then
performed on the bipytz linker in 1 using the reaction illustrated in
Figures 1(b) and S1. It is noted that attempts to obtain 2 from a
mixture of ligand and metal source in solution were unsuccessful
but it was successfully synthesized by treatment of solid 1 with
2,5-norbrnadiene, followed by recrystallizaion of the product from
[a]
Y. Komatsumaru, M. Nakaya, F. Kobayashi, Dr. R. Ohtani, Dr. M.
Nakamura, Prof. S. Hayami
Department of Chemistry, Graduate School of Science and
Technology
Kumamoto University, 2-39-1 Kurokami, Chuo-ku
Kumamoto 860-8555 (Japan)
E-mail: hayami@kumamoto-u.ac.jp
Prof. L. F. Lindoy
School of Chemistry, The University of Sydney, NSW 2006,
Australia
acetone/EtOH.
This
resulted
in
formation
of
[b]
[c]
[Fe(salten)2(bipydz)](BPh4)2·EtOH (2) which, like 1, also showed
gradual SCO behavior, with the slight difference (see later)
observed for the respective spin states at 323 K also reflected in
the results from their respective X-ray structural analysis.
Prof. S. Hayami
Institute of Pulsed Power Science (IPPS)
Kumamoto University, 2-39-1, Kurokami, Chuo-ku
Kumamoto 860-8555 (Japan)
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10.1002/zaac.201800087
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ARTICLE
(a)
(b)
-N2
[Fe2(salten)2(L)]2+
bipytz
bipydz
Figure 1. (a) Structure of [Fe2(salten)2(L)]2+ (L = linker molecule) and (b) the
PSM of the bipytz linker.
Results and Discussion
Single Crystal X-Ray Analysis
The structures of the dinuclear iron(III) compounds 1 and 2
were each determined at 123 and 323 K by single-crystal X-ray
structural analysis (Figure 2 and Table 1), with the structural data
deposited in the CCDC. [14] Both compounds crystallized in the
monoclinic space group P21/c. Each of the two iron(III) ions has
an octahedral coordination geometry composed of the N3O2
donor atoms from a pentadentate salten ligand and an N donor
from a bipytz or bipydz linker. Selected bond lengths and angles
are shown in Table 1. The FeN and FeO bond lengths in 1 span
the range 1.870(2)-2.013(3) Å at 123 K. The average of the FeN
and FeO distances are 1.989 and 1.880, respectively; these are
typical for LS iron(III) compounds incorporating a Schiff-base
N4O2 coordination environment.[15] At 323 K, the FeN and FeO
bond lengths of 1 span the range 1.900(3)-2.139(3) Å, with the
averages of the FeN and FeO distances being 2.094 and 1.970,
respectively. These values are all consistent with those of a
typical HS iron(III) compound incorporating a Schiff-base N4O2-
donor environment. The coordination bond angles are closer to a
regular octahedron upon the spin transition from the HS to the LS
state; both the bond lengths and angles are consistent with the
occurrence of SCO behavior. In 2, the average FeN and FeO
distances are 1.873(2) and 2.013(3) at 123 K, and 1.888(4) and
2.126(5) at 323 K. The presence of a slightly larger HS domain in
1 than in 2 at 323 K was indicated by the sightly larger octahedral
distortion in 1 (Σ = 30.9) around the metal center compared to 2
(Σ = 29.8). Compound 1 has the π-π interactions between BPh4
(C27-C32) and bridging ligand (C26, N5, N6) [centroid-centroid
distance = 3.641 at 123 K]. Compound 2 also has π-π interactions
[centroid-centroid distance = 3.667 Å at 123 K]. Although the
distances of π-π interactions are almost the same, the angles
between the planes constituting the respective aromatic rings are
12.42 ° and 13.85 °, respectively. Compound 2 has larger angles
between planes due to the effect of aromatic ring distortion.
Further details are listed in Table S1. The Fe - Fe distance in one
molecule of the dinuclear complex 1 is 15.341 Å at 323 K and,
for 2 it is 15.309 Å at this temperature (Figures S2, S3).
Figure 2. (a) Crystal structure of (a) 1·EtOH and (b) 2·EtOH. Hydrogen atoms
are omitted for clarity.
Table 1. Representative bond distances and angles for 1 and 2.
Compound
1
2
Temperature (K)
123
323
Bond distance (Å)
123
323
Fe-O(1)
Fe-O(2)
Fe-N(1)
Fe-N(2)
Fe-N(3)
Fe-N(4)
1.890(2)
1.870(2)
1.967(3)
2.013(3)
1.957(3)
1.996(2)
1.900(3)
1.914(3)
2.026(3)
2.107(4)
2.035(3)
2.139(3)
1.889(2)
1.873(2)
1.968(3)
2.013(3)
1.954(3)
1.995(3)
1.902(4)
1.888(4)
2.018(5)
2.099(5)
2.012(5)
2.126(5)
Bond angles (°)
179.1(1)
O(1)-Fe-O(2)
O(1)-Fe-N(1)
O(1)-Fe-N(2)
O(1)-Fe-N(3)
O(1)-Fe-N(4)
O(2)-Fe-N(1)
O(2)-Fe-N(2)
O(2)-Fe-N(3)
O(2)-Fe-N(4)
N(1)-Fe-N(2)
N(1)-Fe-N(3)
N(1)-Fe-N(4)
N(2)-Fe-N(3)
N(2)-Fe-N(4)
N(3)-Fe-N(4)
173.7(1)
88.3(1)
93.2(1)
91.1(1)
87.2(1)
93.1(1)
93.0(1)
88.1(1)
86.6(1)
87.5(1)
174.9(1)
91.1(1)
87.4(1)
178.5(1)
94.0(1)
179.2(1)
89.0(1)
89.5(1)
91.5(1)
89.8(1)
90.3(1)
90.4(1)
89.2(1)
90.3(1)
89.1(1)
178.8(1)
91.4(1)
89.8(1)
179.1(1)
89.7(1)
173.8(2)
88.0(2)
92.6(2)
93.3(2)
86.7(2)
91.0(2)
93.5(2)
88.2(2)
87.3(2)
86.9(2)
175.0(2)
94.2(2)
88.3(2)
178.6(2)
90.6(2)
89.3(1)
89.4(1)
91.6(1)
89.7(9)
89.9(1)
90.4(1)
89.3(1)
90.47(9)
89.8(1)
178.7(1)
91.4(1)
89.8(1)
178.9(1)
89.7(1)
Σ
6.97
30.9
7.8
29.8
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10.1002/zaac.201800087
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ARTICLE
of iron(III), I.S. of 0.24 mm s-1 and Q.S. of 2.09 mm s-1 is assign
to LS state of iron(III) at 85 K. The Mössbauer data show that
~17.5% of the HS domain remains at this lower temperature.
Similarly for 2, two doublet peaks were observed. The doublet
with I.S. of 0.44 mm s-1 and Q.S. of 0.82 mm s-1 is assigned to the
HS state of iron(III), I.S. of 0.24 mm s-1 and Q.S. of 2.09 mm s-1 is
assigned to the LS state of iron(III) at 85K. As the temperature
increases, the ratio of the HS state present also increases. This
change in the ratio is consistent with the observed SCO magnetic
susceptibility results. The value of the isomer shift decreases as
the temperature increases due to the Iinfluence of the second-
order Doppler shift.
Magnetic susceptibility
The temperature dependencies of the magnetic susceptibilities
of 1 and 2 were measured in the temperature range of 5-400 K
The χmT vs. T plots are shown in Figure 3. Gradual one-step SCO
behavior was observed in both cases. The χmT value for 1 was
1.19 cm3 K mol-1 and for 2 it was 1.35 cm3 K mol-1, both at 85 K.
These values are slightly larger than expected for two uncoupled
LS iron(III) ions (0.75 cm3 K mol-1, g = 2) and indicate the
existence of HS domains. Thus the observed plateaux are
consistent with the presence of both HS and LS domains below
100K. On heating, 1 showed gradual incomplete SCO behavior
with the χmT value increasing from 1.19 cm3 K mol-1 at 85 K to
7.48 cm3 K mol-1 at 400 K. Compound 2 also showed gradual
incomplete SCO behavior. For this system the χmT value
increased from 1.35 cm3 K mol-1 at 85 K to 5.93 cm3 K mol-1 at
400 K. These SCO behaviors reflect the presence of a mixture of
HS and LS states, in accord with incomplete SCO between S =
1/2 and S = 5/2. The difference in the χmT values at 400 K for 1
and 2 undoubtedly reflect the influence of different structural and
electronic factors. Intermolecular interactions typically cause an
Electronic spectra
The UV-Vis spectra of bipytz, bipydz as well as of 1 and 2 were
measured in acetonitrile at 25 C (Figure 5a). Generally, it is
known that a Diels-Alder process can be monitored directly
through a color change, corresponding in the present case to the
conversion of bipytz to bipydz.[17] The spectra of bipytz and bipydz
are shown in Figure 5a. In contrast to bipydz, bipytz showed the
expected characteristic absorption at 550 nm arising from the n
 π* electronic transition being observed in the visible region due
to the presence of a low-lying π* orbital.[18] The UV-Vis spectra of
1 and 2 are shown in Figure 5b. The spectrum of 1 exhibits
absorptions at 425 nm (ε = 2675 L / mol cm) and 490 nm (ε =
3007 L / mol cm) while for 2 they occur at 425 nm (ε = 2787 L /
mol cm) and 475 nm (ε = 3123 L / mol cm). These peaks are as
expected for the presence of a mixture of a HS and LS domains
for iron(III).[19] In this case, we could not monitor directly the color
changes between compound 1 and 2 because the weaker
tetrazine n  π* band substantially overlaps the more intense
MLCT absorptions. However, as 1 reacts to form 2, a decrease in
absorption intensity and a shift of the main absorption peak from
490 to 475 nm is seen. It is assumed that these changes are
caused by the PSM reaction as this will undoubtedly influence the
electronics of the adjacent iron(III) centers. However, as might be
anticipated, PXRD determinations showed that the PSM process
only results in minimal changes in the observed patterns for 1 and
2 (Figure S5).
increase in the cooperativity between molecules leading to more
[16]
abrupt SCO behavior.
The presence of π-π interaction
involving the bridging (pillar) ligand is perhaps one of the factors
influencing cooperativity because aromatic ring distortion on
transforming the tetrazine to diazine will decrease intramolecular
orbital overlap and, as
intermolecular π-π interactions. Cooperativities caused by
a consequence, tend to inhibit
intermolecular interaction are more prominent at higher
temperature. This while
1 and 2 show similar magnetic
susceptibilities at low temperature, they show different magnetic
susceptibilities in the higher temperature region, with a steeper
increase in the χmT value for 1. This outcome is concordant with
the bond length and bond angle data from the single crystal
structure determinations discussed earlier.
1.000
(a)
(b)
0.995
1.00
Figure 3. Variable temperature magnetic behavior for 1 and 2.
0.99
1.00
Mössbauer Spectra
The Mössbauer spectra of 1 and 2 were each measured at
three temperatures, with the results shown in Figures 4 and S4,
respectively. The Mössbauer spectra each consist of two doublet
peaks; shown as red and blue traces in Figure 4.
(c)
0.98
-6
-4
-2
0
2
4
6
Velocity / mm s-1
As for 1, the doublet with isomer shift (I.S.) of 0.46 mm s-1 and
Figure 4. Mössbauer spectra for 1 at (a) 300K, (b) 250K (c) 85K.
quadrupole splitting (Q.S.) of 0.87 mm s-1 is assign to the HS state
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10.1002/zaac.201800087
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ARTICLE
by filtration. This product was dispersed in acetic acid (50 mL) and
then 60% HNO3 (10 mL) was added dropwise. The resulting
purple solid was collected by filtration. Finally rectystallized from
pyridine gave 0.55 mg (44%) of purple crystals. 1H NMR (500 MHz,
CDCl3): δ = 8.46 (dd, J(H,H) = 2.9, 6.3 Hz, 2H; CH), 8.90 (dd,
J(H,H) = 2.9, 6.3 Hz, 2H), ppm.
Table 2. Mössbauer parameters for 1 and 2.
Compound
T
[K]
δ
ΔEQ
Γ/2
Area ratio
] [%]
[mms-1
]
[mms -1
]
[mms -1
1
85 HS(FeIII) 0.4632
LS(FeII) 0.2441
0.8698
2.0892
0.3931
0.5484
17.5
82.5
Synthesis of 3,6-bis(4-pyridyl)-1,2-diazine (bipydz)
3,6-Di(pyridine-4-yl)-pyridazine was synthesized by the reported
literature method.[15] 1H NMR (500 MHz, CDCl3): δ = 8.78 ppm (d,
J(H,H) = 5.7 Hz, 2H; CH), 8.00 ppm (dd, J(H,H) = 4.6, 8.0 Hz, 2H;
CH), ppm.
250 HS(FeIII) 0.3373
LS(FeII) 0.2065
0.8662
1.6397
0.4434
0.4599
31.2
68.8
300 HS(FeIII) 0.2999
LS(FeII) 0.2094
0.6227
1.2172
0.4654
0.4365
76.4
23.6
Synthesis of [Fe(salten)2(bipytz)](BPh4)2 (1) (H2salten = 2,2-
[iminobis(3,1-propanediylnitrilomethylidyne)]bis-phenol)
The synthesis of 1 was based on previously reported literature
method.[21] To 3,3-diaminodipropylamine (0.21 g, 2 mmol) in
MeOH (25 mL) was added salicylaldehyde (0.49 g, 4mmol) in
MeOH (25 mL). The resulting mixture was refluxed for 2 h. then
Fe(NO3)3・9H2O (0.81 g, 2 mmol) in MeOH (10 mL) was added
to the yellow solution. To the resulting dark purple solution was
added bipytz (0.13 g, 1 mmol) in MeOH (50mL) and the mixture
was refluxed for 2 h. After cooling the solution to room
temperature, sodium tetraphenylborate (1.03 g, 3 mmol) in MeOH
(10 mL) was added and the solution was stirred for 1 h. The purple
precipitate that had formed was collected by filtration and washed
with ether. Recrystallization of this product from acetone/ethanol
(1:1) gave dark purple crystals. C103H103B2Fe2N12O5.5 (1706.30):
calcd. C 71.50, H 6.00, N 9.71; found C 71.70, H 6.37, N 9.89.
2
85 HS(FeIII) 0.4513
LS(FeII) 0.2465
0.7620
2.1373
0.4226
0.5338
24.6
75.4
250 HS(FeIII) 0.4246
LS(FeII) 0.2268
0.8434
1.6832
0.4221
0.4876
30.6
69.4
300 HS(FeIII) 0.3031
LS(FeII) 0.2243
0.8357
1.4080
0.5335
0.5474
64.3
35.7
[a] δ = isomer shift; ΔEQ = quadrupole splitting; Γ/2 = half-height width of the line
0.10
0.4
Bipytz
Bipydz
1
2
(a)
(b)
0.08
0.06
0.04
0.02
0.00
0.3
0.2
0.1
0.0
Synthesis of [Fe(salten)2(bipydz)](BPh4)2 (2)
Compound 2 was prepared by heating a mixture of 1 and excess
2,5-norbornadiene to 75 C for 17 h. After cooling the reaction
mixture to room temperature, the dark purple product was washed
with ether, and recrystallized from acetone/EtOH (1:1).
C102H104B2Fe2N10O8 (1760.69): calcd. C 70.76, H 6.06, N 8.09;
found C 70.41, H 6.04, N 8.2.
400
500
600
700
300
400
500
600
700
nm
nm
Figure 5. UV-Vis spectra for (a) bipytz and bipydz in chloroform (100 μM), (b) 1
and 2 in acetonitrile (40 μM).
Conclusions
Physical Measurements.
The
dinuclear
tetraazine-containing
SCO
complex
Single-crystal X-ray data for 1 and 2 were recorded on an
Oxford Gemini Ultra diffractometer employing graphite
monochromated Mo Kα radiation generated from a sealed tube (λ
= 0.7107 Å). Data integration and reduction were undertaken with
CrysAlisPro. Using Olex2, the structure was solved with the
ShelXT structure solution program using Direct Methods and
refined with the ShelXL refinement package using Least Squares
minimization. Hydrogen atoms were included in idealized
positions and refined using a riding model. Powder X-ray
diffraction data (PXRD) were collected on a RIGAKU SmartLab
(40 kV/30 mA) X-ray diffractometer using Cu Kα radiation (λ =
1.5406 Å) in the 2θ range of 5°−30° with a step width of 1.0°.
Temperature-dependent magnetic susceptibilities for 1 and 2
between 5 K and 400 K were measured using a superconducting
quantum interference device (SQUID) magnetometer (Quantum
Design MPMS XL) in an external field of 0.5 T. The Mꢀssbauer
spectrometer, with a 57Co/Rh source, was operated in the
transmission mode. Electronic spectra were recorded on a
Shimadzu UV-3600 spectrophotometer. Elemental analyses (C,
H, N) were carried out on a J-SCIENCE LAB JM10 analyser at
the Instrumental Analysis Centre of Kumamoto University.
[Fe(salten)2(bipytz)](BPh4)2 (1) has been synthesized and its
diazine derivative, [Fe(salten)2(bipydz)](BPh4)2 (2), was
generated by PSM. Compound 2 was not able to be obtained from
a mixture of ligand and metal source in solution but could only be
obtained by adding 2,5-norbrnadiene to compound 1 in the solid
state. Relative to compound 1, 2 exhibits a change in its magnetic
behavior that is assigned to electronic influences arising from the
PSM transformation of the tetrazine-containing complex to its
corresponding diazine derivative along with the resulting (small)
differences in the intermolecular and intramolecular interactions
that occur in these structures.
Experimental Section
Synthesis of 3,6-di(pyridine-4-yl)-1,2,4,5-tetrazine (bipytz)
3,6-Di(pyridine-4-yl)-1,2,4,5-tetrazine was synthesized following
the reported literature method.[20] To a solution of 4-cyanopyridine
(1.0 g, 10 mmol) hydrazine monohydrate (6 mL) and deionized
water (1.5 mL) was added concentrated HCl (1.2 mL) dropwise.
The resulting mixture was refluxed for 4 h then cooled to room
temperature and the orange compound that formed was collected
Supporting Information
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10.1002/zaac.201800087
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Crystallographic data, intermolecular distances, temperature
dependence of Mꢀssbauer spectra and Powder XRD patterns.
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Acknowledgements
This work was supported by KAKENHI Grant-in-Aid for
Scientific Research (A) JP17H01200.
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Keywords: Iron(III), Dinuclear, Spin-crossover, Post-
synthetic modification.
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10.1002/zaac.201800087
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Using post-synthetic modification
(PSM) we succeeded in obtaining a
SCO complex that was not able to be
Yuki Komatsumaru, Manabu Nakaya,
Fumiya Kobayashi, Ryo Ohtani, Masaaki
Nakamura, Leonard F. Lindoy and
Shinya Hayami*
-N2
obtained directly from a mixture of
8
ligand and metal source. The complex
6
×
Page No. – Page No.
obtained by PSM showed SCO
4

behavior that differed from that of the
starting complex.
2
Post-synthetic modification for a
dinuclear spin crossover iron(III)
complex
0
0
100
200
300
400
Temperature / K
-N2
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10.1002/zaac.201800087
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
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