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22 September 2000

Chemical Physics Letters 328 Ž2000. 188–196


www.elsevier.nlrlocatercplett

Spin crossover in iron žII / tris ž2-ž 2-pyridyl /benzimidazole/ complex


monitored by the variable temperature EXAFS
ˇ a,) , Martina Vrbova´ a, Rudiger
Roman Boca ¨ Werner b, Wolfgang Haase b
a
Department of Inorganic Chemistry, SloÕak Technical UniÕersity, SK-812 37 BratislaÕa, SloÕakia
b
Institute of Physical Chemistry, Darmstadt UniÕersity of Technology, D-64287 Darmstadt, Germany
Received 1 June 2000; in final form 2 August 2000

Abstract

Standard EXAFS equipment has been utilized in conducting the variable temperature experiments using the
wFeŽpybzim. 3 xŽClO4 . 2 P H 2 O sample, pybzim being a bidentate 2-Ž2-pyridyl.benzimidazole ligand. There is a jump in the
metal–ligand ŽFe–N. distance comparable with the step in the effective magnetic moment. The distance increases from 1.95
˚ In the transition region, the error bars are much broader than before and after this region. The transition
to 2.11 A.
temperature taken from the fittings is 132 K, which is about 9 K lower than that from magnetic susceptibility measurements.
q 2000 Published by Elsevier Science B.V.

1. Introduction powder samples. Such an investigation is the subject


of the present study. In contrast to the X-ray data,
Monitoring of the spin crossover Žlow-spin to which were collected only at two temperatures Žbe-
high-spin transition. may be done by several experi- low and above the transition temperature., the EX-
mental techniques w1–5x. Most frequently the vari- AFS data were scanned continuously, at 32 different
able temperature magnetic susceptibility measure- temperatures. This allows a dense mapping of the
ments are applied showing a jump of the effective structural changes during the spin crossover, which
magnetic moment at the transition temperature. may help in developing more complete theoretical
Analogous information, however, can be drawn from models of the spin crossover phenomenon. In paral-
¨
the Mossbauer spectra, variable temperature infrared lel to the theories that embody the macroscopic
ŽIR. spectra, electron spectra, calorimetric measure- parameters Žthe elastic bulk modulus, the Poisson
ments, etc. The X-ray structure data on single crys- ratio w6x. an alternative theory could be based upon
tals show that the metal–ligand bond lengths in- the microscopic parameters Žharmonic potential char-
crease by ca. 15% during the spin crossover. Similar acterized by the equilibrium distances and the force
information may be drawn from EXAFS data on constants.; for that reasoning the detailed informa-
tion about the structural changes within the chro-
mophore are ultimate.
)
Corresponding author. Fax: q421-52431-98; e-mail: The spin crossover in the complex under study –
boca@cvtstu.cvt.stuba.sk wFeŽpybzim. 3 xŽClO4 . 2 P nH 2 O has been reported sev-

0009-2614r00r$ - see front matter q 2000 Published by Elsevier Science B.V.


PII: S 0 0 0 9 - 2 6 1 4 Ž 0 0 . 0 0 9 0 2 - 7
ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
R. Boca 189

package w14x. The amplitude and phase functions


which are needed for fitting the x Ž k . data were
obtained from simulations of the EXAFS function of
th e lo w -s p in Ž a t 2 9 8 K . c o m p o u n d
wFeŽbzimpy. 2 xŽClO4 . 2 P 0.25H 2 O for which the struc-
Fig. 1. Sketch of the structure of the bidentate ligand pybzim Žleft. ture data have been presented elsewhere w15x and
and the tridentate ligand bzimpy Žright.. showing R 1ŽFe–Npy . s 1.87 and R 2 ŽFe–N bzim . s
1.99 = 10y1 0 m.
In principle there are six different Fe–N distances
eral times w7–12x so that the system is well character- with six different Debye–Waller factors. Together
ized. Both the magnetic susceptibility data and the with the E0 shift, the reduction factor and the coordi-
¨
Mossbauer spectra show the spin transition at nation numbers of each shell, we have 20 variables,
Tc s 141 K for the monohydrate. However, the sam- which is too much for fitting. Therefore some simpli-
ple shows a variable content of crystal water and a fications have been introduced: Ži. the E0-shift was
different amount of an underlying paramagnetism determined Žfitted. ones at lowest temperature, for all
due to the presence of the paramagnetic impurity that other temperatures this fitted value was taken as a
grows with the sample aging. fixed parameter; Žii. six Fe–N distances were dis-
The structure of the bidentate ligand Žpybzim. is tributed into two shells for which different Debye–
shown in Fig. 1 along with an analogous tridentate Waller factors were considered. Consequently only
ligand Žbzimpy. whose complex was used during the five variables to be optimized survive: the distances
data analysis. R 1ŽFe–Npy . and R 2 ŽFe–N bzim ., the corresponding
Debye–Waller factors s 1 and s 2 , and the amplitude
reduction factor.
2. Experimental
2.3. Magnetic susceptibility measurements
2.1. Sample preparation
Temperature dependence of the magnetic suscep-
The ligand pybzim Žs 2-Ž2-pyridyl.benzi-
tibility has been measured using the Faraday-type
midazole. and its FeŽII. complex was prepared
balance at the applied field of B s 1.4 T. A correc-
according to the literature w11,13x. Anal. Calc. for
tion for the underlying diamagnetism has been calcu-
C 36 H 27 Cl 2 FeN9 O 8 P H 2 O, hereafter 1, Žfound.: C,
lated using the set of Pascal constants.
50.4 Ž51.1.; H, 3.4 Ž3.5.; N, 14.7 Ž14.7.%.

2.2. EXAFS measurements and analysis


3. Results and discussion
The sample for the EXAFS measurements was
prepared in the form of a pellet in which the grounded The results of the EXAFS analysis for a single
complex Žca. 50 mg. with the double amount of temperature are exemplified in Fig. 2. It can be seen
special polyethylene powder were pressed into a pill that the fitting the EXAFS function is quite satisfac-
Ždiameter, 13 mm; height, ca. 1 mm.. The sample tory.
was exposed to standard equipment in the HASY- The temperature dependence of the metal–ligand
LAB at DESY ŽHamburg, beamline E4, resolution distances R 1 and R 2 is shown in Fig. 3 Žleft.. An
1 eV.. assignment whether R 1 belongs to Fe–Npy or Fe–
The EXAFS spectra were measured on the iron N bzim is impossible on the basis of the EXAFS data
K-edge at 32 different temperatures between 50 and alone. However, relying to the analogy with the
300 K with smaller steps in the region of the spin low-spin complex wFeŽbzimpy. 2 xŽClO4 . 2 P 0.25H 2 O
crossover. The raw data were manipulated with the we assume that the low-temperature data on 1 could
programs AUTOBK and FEFFIT from the UWXAFS be assigned as R 1ŽFe–Npy . - R 2 ŽFe–N bzim .. The
190 ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
R. Boca

Fig. 2. Experimental Žsolid. and calculated Ždashed. Fourier transform of the EXAFS function for 1 at 90 K.

temperature dependence of the Debye-Waller factors The corresponding plot is displayed in Fig. 4 Žright..
s 1 and s 2 is shown in Fig. 3 Žright.. The discrep- The evident non-linearity around ln K s 0 shows
ancy factor of the fit presented at the same place that a simple Boltzmann equilibrium is violated so
shows the reliability of the extracted data. that the spin transition in the present case is influ-
The temperature dependence of the averaged enced by some degree of cooperativity.
metal–ligand distance RŽFe–N. is shown in Fig. 4 Among a variety of spin crossover model the
Žleft.. The distance increases from 1.95 to 2.11 A ˚ Ising-like model has been utilized in the numerical
with a jump centered at 132 K. In the transition analysis. It is based on the Hamiltonian
region, the error bars are much greater Ž"0.07 A ˚.
than before and after this region "0.015 A .
Ž ˚ . Hˆ s Ž D0r2 . sˆ y J² s :sˆ Ž 3.
Lower Ž R LS . and upper Ž R HS . limits of the inter-
atomic distances were used in calculating the conver- that accounts for the site formation energy D0 , and
sion curve – the high-spin mole fraction Ž x HS . ver- the spin–spin interaction taken in the mean-field
sus temperature according to the formula approximation. Here the fictitious spin sˆ adopts
R T y R LS values of y1 for low-spin and q1 for the high-spin
x HS s . Ž 1. state, respectively. Its thermal average, ² s :, is di-
R HS y R LS rectly related to the high-spin mole fraction: x HS s
Such a function is presented in Fig. 4 Žcenter.. Ž1 q ² s :.r2. The essential features of such a model
The transition temperature read off at x HS s 0.5 is are well described elsewhere w16–20x. Consequently
Tc s 132 K. an implicit equation is to be iterated
Finally an Arrhenius plot was generated, i.e. ln K
y1 q f Ž ² s : .
versus 1rT function where the low-spin to high-spin ²s :s . Ž 4.
equilibrium constant was calculated as follows: 1 q f Ž ² s :.
x HS
Ks . Ž 2. In the simplest version the function f Ž² s :. is
1 y x HS expressed in the form
In these calculations an eventual contamination of
the sample by FeŽIII. impurities has been ignored. f s reff exp y Ž D0 y 2 J² s : . rkT Ž 5.
R. Boca
ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
Fig. 3. Temperature dependence of the fitted EXAFS data: Žleft. metal–ligand distances R1 Žcircles., R 2 Žsquares., R Žtriangles.; Župper right part. Debye–Waller factors; Žlower
right part. discrepancy factor of the fit.

191
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R. Boca
ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
Fig. 4. EXAFS data: temperature dependence of the averaged Fe–N distances for 1 with error bars Žleft.; high-spin mole fraction Žcenter.; an Arrhenius plot Žright.. Open
symbols, experimental data; full points, calculated data based on the fit of the high-spin mole fraction.
ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
R. Boca 193

where the effective degeneracy ratio, reff s rel r vib ) The amount of PI has been determined by fitting
5, accounts for the electronic as well as vibrational the low-temperature ŽLT. magnetic data to the
contribution Ž rel s 5.. In a more advanced treatment Curie–Weiss function,
the vibrational contribution is averaged over m-ac- xmol Ž LT . s x PI x PI
tive modes Ž m s 15 for a hexacoordinate complex. 2
and thus w18x s x PI C0 g PI SPI Ž SPI q 1 . r3 r Ž T y Q PI . .
m Ž 8.
1 y exp Ž hn LS rkT .
½
f s rel
1 y exp Ž hn HS rkT . 5 Ž C0 s NA m 0 m 2B rk comprises the fundamental physi-
cal constants in their usual meaning. by assuming
that for an FeŽIII. center the values of S PI s 5r2 and
= exp  y m Ž hn HS y hn LS . r2
g PI s 2.0 can be safely fixed. Then Q PI s y4.53 K
qD0 y 2 J² s : rkT 4 . Ž 6. and x PI s 0.0269 resulted.
The subsequent analysis relies on the balance
ŽThe temperature variation of the vibrational contri- x T s x LS x LS q x HS x HS q x PI x PI Ž 9.
bution dominates at low temperatures and modifies
the linearity of the Arrhenius plot.. During the fitting and the normalization of the mole fractions
procedure Eq. Ž4. needs to be iterated for each 1 s x LS q x HS q x PI . Ž 10 .
temperature and a trial set of parameters D0 , J, reff Under these assumptions, the following equations
andror hn HS and hn LS . are fulfilled
As a result of the fitting Žthe discrepancy factor
RŽ x HS . s 0.051 for all 32 data points. the final set
Ž x T T . y Ž x LS T . Ž 1 y x PI . y Ž x PI T . x PI
x HS s ,
of the spin-crossover parameters resulted: D0rk s Ž x HS T . y Ž x LS T .
1847 K, Jrk s 127 K, hn HS rk s 400 K, and Ž 11 .
hn LS rk s 609 K. Of main interest is the cooperativ-
ity parameter J which adopts a considerable value. and
Its positive sign means that the given center prefers x HS x HS
Ks s . Ž 12 .
neighbours of the like spin. Just this parameter is x LS 1 y x HS y x PI
responsible for the non-linearity of the Arrhenius Having x PI already determined, and assuming
plot around ln K s 0. Being, however, below the that x LS s 0 for the diamagnetic S s 0 state, the
critical limit, Jrk - Tc , no thermal hysteresis effect evaluation of x HS s f ŽT . and ln K s f Ž1rT . func-
occurs. tions is an easy task provided that the Ž x HS T .
The magnetic susceptibility recorded on the same product is read-off as the maximum of the experi-
sample has been converted to the effective magnetic mental values ŽFig. 5 Žcenter and right... Based on
moment, calculated as these plots, one can conclude that the magnetic data
X
meffrm B s 798 Ž xmol T.
1r2
. show similar, although not identical, behaviour of
Ž 7.
the spin crossover when compared to EXAFS data.
Its temperature dependence is shown in Fig. 5 The transition temperature is about 9 K higher,
Žleft.. Tc s 141 K, which nicely matches with earlier mag-
The value of meffrm B f 1.0 below 70 K indicates ¨
netic susceptibility and Mossbauer spectra investiga-
the presence of a paramagnetic impurity ŽPI.. This is tions w11,12x. Again a cooperativity effect is well
the only source of the paramagnetism at low temper- evident around ln K s 0.
ature and in no case it could be ignored as far as the The fitting procedure based on magnetic data has
magnetic data are concerned. been applied to the magnetic susceptibility function

2 2
x T s x HS x HS q x PI x PI s w Ž 1q² s : . r2x C0 g HS w SHS Ž S HS q1. r3 x r T q x PI C0 g PI w SPI Ž SPI q1. r3x r Ž T y Q PI . Ž 13 .
194
R. Boca
ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
Fig. 5. Magnetic susceptibility data: temperature dependence of the effective magnetic moment for 1 Žleft, inset: magnetic susceptibility in 10 9 m3 moly1 .; high-spin mole
fraction Žcenter.; an Arrhenius plot Žright.. Open circles, experimental data; full points, calculated data based on the fit of the magnetic susceptibility.
ˇ et al.r Chemical Physics Letters 328 (2000) 188–196
R. Boca 195

with SHS s 2; g HS is taken as a free parameter. Here Acknowledgements


Eq. Ž4. again is iterated for each temperature and a
trial set of the spin crossover parameters. DFG is acknowledged for financial support and
Since the low-temperature data interfere with the the HASYLAB for the beam-time. R.W. acknowl-
strong signal of the paramagnetic susceptibility, a edges TU Darmstadt for support during Ph.D. study.
reliable determination of hn HS and hn LS is dis-
abled. As a result of the fitting Žthe discrepancy
factor RŽ x . s 0.015 for 53 data points. the mag- References
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