Distinct molecular motions in a switchable chromophore dielectric 4-N,N-dimethylamino-4'-N'-methylstilbazolium trifluoromethanesulfonate

Article abstract of DOI:10.1002/adfm.201201770

Molecular motion associated with rotational and orientational phase transitions is one of the prominent structural strategies for assembling the functional materials such as artificial motors and tunable molecular dielectrics. Here, a new organic chromophore molecule, 4-N,N-dimethylamino-4'- N'-methylstilbazolium trifluoromethanesulfonate (complex 1), which undergoes an exceptional order-disorder phase transition at 322 K, is successfully synthesized. The single crystal X-ray diffraction analysis, thermal analysis, and dielectric measurements are used to characterize its dielectric dynamic behaviors. The results reveal that 1 behaves as a molecular rotator with the obviously distorted bipyramidal geometry of trifluoromethanesulfonate anions. In addition to its disorderings, two very distinct motions of the anionic moieties are confirmed, namely the "earth rotation" of partial units and the "earth revolution" of the whole molecule. Such unique molecular motions are found to be mainly responsible for the order-disorder phase transition together with the abrupt dielectric anomaly and anisotropy. The charge-transfer cationic parts enhance the molecular motions behaving as the stator and give rise to its excellent third-order nonlinearities. The concept may allow for the remote control of molecular events to explore functional materials in organic chromophores.

Full text of DOI:10.1002/adfm.201201770

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Distinct Molecular Motions in a Switchable Chromophore
Dielectric 4-N,N-Dimethylamino-4′-N′-methylstilbazolium
Trifluoromethanesulfonate
Zhihua Sun, Junhua Luo,* Tianliang Chen, Lina Li, Ren-Gen Xiong, Ming-Liang Tong,
and Maochun Hong
researchers, owing to the potential appli-
cation in data communication, signal
processing and sensing, and rewriteable
optical data storage, etc.[2] Though much
progress had been achieved in designing
sophisticated small molecular analogue
machines,[3] the major challenge is to
regularly control the motions of the dipole
moments with principle. One of the most
promising strategies is to assemble com-
plex functional materials that possess
molecular-level properties and functions
in a collective manner at the macroscopic
scale.[4] For example, the 180° fl ip-flop
molecular random motion of a rotatory
unit could give rise to a rotation of the
local structure, resulting in the formation
of phase transition from high-temperature
disordered state to low-temperature
ordered state.[5] Unorientational motion
of partial units within the range of 30°
was also observed during the ferroelectric
phase transition.[5]
Molecular motion associated with rotational and orientational phase transi-
tions is one of the prominent structural strategies for assembling the func-
tional materials such as artificial motors and tunable molecular dielectrics.
Here, a new organic chromophore molecule, 4-N,N-dimethylamino-4′-N′-
methylstilbazolium trifluoromethanesulfonate (complex 1), which under-
goes an exceptional order-disorder phase transition at 322 K, is successfully
synthesized. The single crystal X-ray diffraction analysis, thermal analysis,
and dielectric measurements are used to characterize its dielectric dynamic
behaviors. The results reveal that 1 behaves as a molecular rotator with
the obviously distorted bipyramidal geometry of trifluoromethanesulfonate
anions. In addition to its disorderings, two very distinct motions of the ani-
onic moieties are confirmed, namely the “earth rotation” of partial units and
the “earth revolution” of the whole molecule. Such unique molecular motions
are found to be mainly responsible for the order–disorder phase transition
together with the abrupt dielectric anomaly and anisotropy. The charge-
transfer cationic parts enhance the molecular motions behaving as the stator
and give rise to its excellent third-order nonlinearities. The concept may allow
for the remote control of molecular events to explore functional materials in
organic chromophores.
Recently, Collet et al. had discovered the
novel ferroelectric structural order in the
pure organic charge-transfer (CT) crystal
at the molecular level.[6] Surprisingly, a series of configura-
tional-locked polyene organic chromophores were synthesized
with unique reversible phase transition from a low-temperature
higher symmetry to the high-temperature lower symmetry.[7] As
one of the most outstanding CT framework, hemicyanine dye
of the stilbazolium chromophore was used to assemble poten-
tial ferroelectrics with above-room temperature phase transi-
tion.[8] However, to our knowledge, the microscopic mechanism
of such phase transitions and the concomitant solid-solid struc-
tural transformations were not fully understood. Encouraged
1. Introduction
Molecular motions associated with phase transition have been
explored in a wide range of materials and may greatly affect
their properties. Utilizing the exciting possibility of dynamic
and related behavior caused by rotational or orientational
motion, molecular rotator has been used to assemble the
artificial molecular machines such as shuttles, brakes, tweez-
ersand and potential molecular dielectrics.[1] Among them,
dielectric switching complex has attracted great attentions for
Dr. Z. Sun, Prof. J. Luo, T. Chen, L. Li, Prof. M. Hong
Key Laboratory of Optoelectronic Materials
Chemistry and Physics
Prof. R.-G. Xiong
Ordered Matter Science Research Center
Southeast University
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences
Fuzhou, Fujian 350002, China
Nanjing 210096, China
Prof. M.-L. Tong
State Key Laboratory of Optoelectronic
Materials and Technologies
School of Chemistry and Chemical Engineering
Sun Yat-Sen University
E-mail: jhluo@fjirsm.ac.cn
DOI: 10.1002/adfm.201201770
Guangzhou 510275, China
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CH3
N
Methanol
CH3I
+
H3C
N CH3
I
Methanol
Piperidine
N
CHO
Methanol
CF3SO3Ag
N
N
N
CH3
N
I
CH3
CF3SO3
Scheme 1. The synthesis routine of 1.
by the pioneering work, herein, we presented a new switchable
molecular dielectric based on the CT stilbazolium chromo-
phore, 4-N,N-dimethylamino-4′-N′-methylstilbazolium trif-
luoromethanesulfonate (complex 1), with a reversible phase
transition utilizing the molecular motion of trifluorometh-
anesulfonate anionic moiety. For 1, its anion acts as a rotator
while the chromophore cation behaves as the stator-like part
during phase transition. With the enhanced stabilization of
cation, exceptionally distinct mechanical motions of the anionic
moieties were firstly observed, i.e., the “earth rotation” of partial
units and the “earth revolution” of the whole molecule.
saturated solution was hermetically kept at 5–6 °C above its sat-
urated temperature for 24 h. With decreasing the solution tem-
perature to its saturated status, the perfect seed-crystal obtained
by the spontaneous nucleation was dipped into solution. Before
crystal growth, the seed-crystal was maintained in the solution
slightly above saturated status for homogenization. The tem-
perature-lowering rate for crystal growth was 0.05 °C/day. The
straightforward fabrication of bulk crystals with high optical
qualities guarantees its potential device application. The purity
of the as-grown crystals was confirmed by the IR spectrum,
element analysis and X-ray powder diffraction matching with
the single-crystal structural determination at room temperature
(see Supporting Information Figure S1,S2).
2. Results and Discussion
Differential scanning calorimetry (DSC) measurement was
used to detect phase transition and to confirm the existence of
heat anomaly. As shown in Figure 2a, a sharp endothermic peak
Complex 1 was synthesized by the ion-exchange reaction of
trifluoromethanesulfonate silver and 4-N,N-dimethylamino-4′-
N′-methylstilbazolium iodide, which was prepared from 4-pico-
line, methyl iodide and 4-N,N-dimethylamino-benzaldehyde in
the presence of piperidine as catalyst (Scheme 1). Large-size
crystals were successfully grown from the methanol solutions
as the red plates perpendicular to the c-axis by the temperature
lowing method (Figure 1). In the growth commencement, a
appearing at the phase transition temperature (T = 322 K) and
c
the relative large heat hysteresis (≈6 K) were clearly recorded,
which indicate that complex 1 undergoes a first-order phase
transition.[9] Entropy change ΔS accompanying the transition
was estimated as ≈6.4 J mol−1 K−1 . Given that ΔS = nRlnN,
where R is the gas constant and N is the ratio of possible config-
urations in the disorder system, it obtains N = 2.1, which indi-
cates the order–disorder transition undergoing reorientations
at two sites.[10] Furthermore, the sharp heat capacity peak also
corresponds well to the phase transition in the heating mode.
From the specific heat vs temperature curve, the respective ΔS
and N are approximately calculated as 6.56 and 2.2, coinciding
fairly well with the DSC results and further confirming the typ-
ical order-disorder transition.
What greatly favors its potential application as the switchable
molecular dielectric is that its melting temperature is far beyond
T , approaching 484 K as shown in the thermal analysis curves
c
(Figure 2b). Such a large temperature gradient (≈162 K) between
phase transition and melting point makes 1 possess great
advantage to be fabricated into the applicable device. For con-
venience, we label the phase at 343 K as the high-temperature
phase (HTP), the phase at 293 K as the room-temperature
Figure 1. The as-grown crystals of 1 with the respective 3D sizes of 4.8 ×
4.5 × 3.2 mm3 and 4.1 × 4.0 × 2.6 mm3.
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(a)
even the temperature increases far away from the critical point,
which is also confirmed from the variable-temperature XRPD
patterns. Thus, it is difficult to describe the phase transition
with a proper Aizu notion. Using Landau’s phenomenological
approach,[12] the metastable phases may coexist with the parent
phase in the first-order phase transition arousing a thermal
hysteresis. Perhaps, HTP for 1 is such a metastable phase even
far away from the critical point.
0.6
0.3
0.0
-0.3
-0.6
1.8
0.8
1.5
1.2
0.9
0.4
Heating
HTP
0.6
20 30 40 50 60 70 80
Temperature (oC)
RTP
0.0
-0.4
-0.8
Figure 3a shows the molecular crystal structures of 1 at RTP
and HTP. In the organic cation, the main part of π-conjugated
bridge from (CH3)2N- group to pyridinium acceptor exhibits
as a planar mirror.[13] The striking feature of its packing is that
the polar polymer-like cations are stacked up along the b-axis,
and anions link them together utilizing weak hydrogen bonds
(Supporting Information Figure S3). As checked by PLATON,
CϪH···O hydrogen bonds are the main molecular interactions
HTP
RTP
Cooling
-40
-20
0
20
40
60
80
o
Temperature
(
C
)
−
in addition to the van der Waals force. Oxygens of CF3SO3
(b)
100
80
anions are involved in bifurcated hydrogen bonds acting as
the acceptor. One direction corresponds to C5H4ΝϪCH3···O2
group and the other links carbon atom of pyridine ring. At
room temperature, the trifluoromethanesulfonate anions
exhibit almost ordered and ideal tetrahedral geometry of bipy-
ramidal. Contrarily, symmetry of both pyramidals is broken
upon higher temperature, revealing the existence of a highly
disordered anion. Thus, the phase transition is confirmed as
an order-disorder type, matching very well with the crystallo-
graphic data and DSC results.
In order to further confirm the above-mentioned phase
transition, variable-temperature X-ray powder diffraction was
performed on the polycrystalline samples of 1. The compara-
tive spectra (Figure 4) indicate that the phase transition occurs
above 322 K. All the diffraction patterns coincide fairly well
with the simulated ones at different temperatures (Supporting
Information Figure S2).
Severe changes of physical properties approaching critical
point could also support the phase transition. Here, dielectric
experiments of the complex relative permittivity were per-
formed on crystal samples of 1. All the faces were selected in
accordance with the RTP structure. In the heating mode, both
the dielectric constants and loss along all the directions keep
stable until the temperature reaches 322 K (Figure 5). Subse-
quently, the permittivity exhibits an obvious increase followed
by a clear slope and then remains almost constant, indicating
the appearance of phase transition. What interests us is the
existence of a tiny dielectric relaxation process at different
frequencies, indicating a relatively slow dipolar motion of the
huge organic molecule of 1. Similarities have been examined
for some other stilbazolium compounds.[8] Macroscopic relaxa-
tion time was roughly estimated from the frequency depend-
ence of ε′ at the inflection point of the curves. For a Debye
peak, the condition for the peak is 2πτf = 1 and the detailed
relationship can be described by the Arrhenius equation, lnf =
−ln(2πτo) − Ea/RT, where T is the temperature and f is the vibra-
tion frequency. Thus, the activity energy Ea and relaxation time
τo can be estimated according to the experimental data of lnf vs
1/T. The average Ea and τo for 1 are approximately calculated
to be 96 kJ/mol and 1.5 ×10−4.5 s, respectively. The magnitude
value of Ea is similar to that of other compounds (usual value
≈10 to 70 kJ/mol).[14] The cooperative motions and the steric
2.4
1.8
1.2
0.6
0.0
-0.6
TG
decomposition point
60
DTA
40
melting point
phase transition point
20
50 100 150 200 250 300 350 400 450 500
Temperature (oC)
Figure 2. DSC measurements obtained on a heating-cooling cycle (a) and
the TG/DTA curves of 1 with heating rate 10 °C/min (b). Temperature
dependence of the specific heat (Cp) deduced from DSC data in the
heating mode is shown in the inset of (a).
phase (RTP). Crystal structures were also resolved at 338 K
(ITP) and 93 K (LTP) for forthcoming comparative investiga-
tion.[11] Variable-temperature X-ray single-crystal diffraction
reveals that 1 crystallizes in the centrosymmetric space group
P21/c in RTP with cell parameters of a = 17.508(5), b = 7.607(2),
c = 13.533(4) Å, β = 93.712(6)° and V = 1798.4(10) Å3. As to
LTP structure, it adopts the same structure as that in RTP
and little difference can be seen by comparing the crystal
data, suggesting that there is no occurrence of phase transi-
tion between 293 and 93 K. However, what interests us is the
crystallographic transformation from RTP to HTP. Though its
HTP still belongs to P21/c space group, β becomes to 90.05°
almost possessing the orthorhombic feature, and the detailed
cell parameters are a = 7.190(9), b = 7.698(10), c = 34.08(4) Å
and V = 1886(4) Å3. Except for the consensus of b-axis length,
all the values of a-, c-axis lengths and β angle change mark-
edly owing to the phase transition. According to the traditional
phase transition theory, the RTP structure usually adopts a sub-
group of HTP, namely the HTP for 1 should be determined
in an orthorhombic system with higher symmetry operations.
However, its structure still persists in the monoclinic system
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Figure 3. The molecular units of 1 in RTP and HTP with the trifluoromethanesulfonate anion disordered in the HTP (a). The packing structures are
viewed along the b-axis with the phase transition from RTP to HTP (b). Symmetry breaking occurs in the ordered and ideal bipyramidal of trifluoro-
methanesulfonate anion, originating from the reversible phase transition.
hindrance of huge organic molecules for 1 might contribute to
slightly higher activity energy.
In addition, the dielectric permittivities of 1 present a striking
anisotropy along the different crystallographic axes. In the HTP,
values of dielectric permittivity at 5 KHz along [001] direction
are three- and four-times larger than those along [020] and
[−100] directions respectively, while the corresponding values
in RTP allow for the dielectric anisotropy of ε′c/ε′b = 4.2 and
ε′c/ε′a = 3.8. To our best knowledge, such a
large temperature-independent dielectric ani-
sotropic behavior is rarely reported in the pure
organic complex. Furthermore, a stronger
anomaly was observed in the c-axis direction,
compared with a smaller one recorded along
the two-fold axis direction. Xiong et al. quali-
tatively explained the dielectric anisotropy of a
nickel(II) complex.[15] Herein, we propose that
such a strong dielectric anisotropy mainly
depend on the intrinsic structural diversifica-
tion upon high temperature. It can be seen
from the crystal structures that c-axis length
exhibits an extremely larger variety than both
a-axis and b-axis with the increasing tempera-
ture, which clearly shows that c-axis is much
more sensitive to the external stimuli espe-
cially at low frequency, in good agreement
with switchable dielectric character. Other-
wise, the planar organic cation lies almost
perpendicular to the b-axis in the RTP. Con-
sidering the equivalent effect induced by the
anions, the unidirectional CT in the organic
plane will yield smaller dipole-moment along
the b-axis, hence leading to less change of
dielectric permittivity in this direction. The
Figure 4. The variable-temperature X-ray powder diffraction patterns of 1.
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To obtain further insights into the microscopic origin of the
phase transition for 1, its structural transformation of anionic
moieties was shown in Figure 6, together with the tempera-
ture dependence of theoretical order parameter. In the RTP,
all the F atoms in the anion occupy the pyramidal vertex with
equivalent CϪF bonds (≈1.3 Å) and FϪCϪF angles (≈107°),
suggesting the existence of an ordered pyramidal. Similarly,
the O atoms also locate harmoniously in the other pyramidal
(Supporting Information Table S1). Thus, the trifluorometh-
anesulfonate anion exhibits the ordered and ideal tetrahedral
geometry of bipyramidal. With the temperature increasing
into HTP, the symmetry-breaking occurs accompanied with
the disequilibrium of CϪF and SϪO bonds. As the arrows
indicate, both contraction and elongation of bonds occur and
distort the ideal pyramidal, constructing a highly disordered
anion. The sharp decline of order parameter approaching Tc
would also strongly support the order-disorder phase transi-
tion.[17] In addition to the dynamical disorderings, another
strikingly interesting feature is to observe two distinct types
of molecular motions of the anionic moiety, i.e., the earth
rotation of partial units around S1ϪC17 bond and the earth
revolution of the whole molecule. As shown in Figure 7, the
–SO3 polyhedron rotates anticlockwise while–CF3 polyhedron
behaves in the clockwise rotation. Such a motion is described
like the earth rotation, which is supported by the detailed
data of FϪCϪF and OϪSϪO angels in Table S1 (Supporting
Information). Meanwhile, the anionic moiety also revolves
referring to the cation plane which is an excellent D-π···A
planar CT chromophoric framework. When temperature
increases, the ϪSO3 tetrahedron falls towards the plane while
the –CF3 polyhedron uplifts away from the plane, resulting in
the orientational motion of the whole molecule. Namely, the
stilbazolium cation functions as a stator which favors to the
motions of anion-rotator. The included angle between S1ϪC17
line and cation plane would clearly depict such a motion like
the earth revolution. In LTP, the included angle is calculated
as 60.5° between the rotation axis and cation plane, while the
corresponding value becomes 9.3° in HTP. Hence, the 51.2°
orientational motion of anionic moiety occurs, leading to the
macroscopic phase transition together with the structural dis-
tortion. As we are aware, this is the first observation of such
interesting motions triggered by the increasing temperature
during the phase transition.
80
(a)
500 Hz
1 KHz
5 KHz
10 KHz
100 KHz
60
(001)
1 MHz
40
20
(020)
20
30
40
50
60
(°C)
70
80
Temperature
12
10
8
(b)
Cp5KHZ
Cp10KHZ
Cp100KHZ
Cp1MHZ
(-100)
6
30
35
40
45
50
55
60
65
Temperature
(°C)
2.5
2.0
1.5
1.0
0.5
(c)
500 Hz
1 KHz
5 KHz
10 KHz
100 KHz
1 MHz
The comparative structure analysis indicates the cationic moiety
seems to make no contribution to the phase transition. However,
the weak hydrogen bonds are sensitive to heat and may have a sig-
nificant impact on its properties.[18] For example, the distance of
C14-H···O2 changes from 3.178 Å to 3.338 Å when comparing its
RTP and HTP. This thermal-induced elongation effect may also
response for the activation of molecular freedom degree or order
parameter, because it generates an increase in the ionic displace-
ment similar to other compounds.[19] Most probably, the weakness
of hydrogen-bonded interaction favors the anionic rotation and
enhances the cationic CT process. Here, ab initio calculations at
RHF/3-21G∗ level show that molecular HOMOs mainly localize
in 4-N-styryl while LUMOs in cationic pyridinium ring and the
bridge, giving a significant charge displacement from benzenium
to pyridinium-ring (see Supporting Information Figure S4-S6).
The HOMO-LUMO energy gap ΔEHL is theoretically estimated
20
30
40
50
60
70
Temperature (°C)
Figure 5. a,b) Temperature-dependent dielectric constants of 1 on crystal
samples along the different crystallographic directions of (001), (020),
and (-100). The dielectric loss as the function of temperature along (001)
direction is presented in (c).
variation of permittivities along the direction perpendicular to
molecular plane matches well with dielectric behaviors of some
substances with free- and frozen-rotator phases.[16]
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mined as 1.585 × 10−19 m2/W and −2.621 ×
10−12 m/W. The modulus of effective third-
order susceptibility χ(3) and second molecular
hyperpolarizability γ are calculated as 5.086 ×
10−13 esu and 3.998 × 10−31 esu (Supporting
Information Table S2), revealing its potential
application as a third-order NLO candidate.
3. Conclusion
In conclusion, the present work has suc-
cessfully demonstrated a new switchable
molecular dielectric, which undergoes an
exceptional order-disorder phase transition
at 322 K. The distorted trifluoromethanesul-
fonate anion behaves as the molecular-rotator
while the chromophore cation acts as the
stator-like part. Besides the disorderings, two
exceptionally distinct molecular motions were
observed in the anionic moieties, namely the
earth rotation of partial units and the earth
revolution of the whole molecule. Above the
critical point, the anionic moiety exhibits an
unprecedented 51.2° orientational motion
together with the structural distortion. The present work has
revealed a previously undescribed feature of molecular motions
and we believe the findings will urge exploration for new multi-
functional materials in organic chromophores.
Figure 6. Dynamical order–disorder transformation of anionic moieties at RTP and HTP with
the temperature dependence of theoretical order parameter (Q). RTP shows the ordered and
ideal tetrahedral geometry of bipyramidal, while the symmetry-breaking occurs in HTP.
to be 5.032 eV, much larger than experimental result from its
absorption spectra. Experimental Z-scan reveals a strong NLO
absorption, regarded as saturable absorption. The NLO refractive
index (n2) and absorption coefficient (β) were respectively deter-
Figure 7. Schematic illustration of the exceptionally distinct molecular motions triggered with the phase transition. The cation plane acts as a stator-
like part while the anionic moiety behaves as a rotator.
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445, 523; d) J. V. Hernández, E. R. Kay, D. A. Leigh, Science 2004,
306, 1532; e) S. P. Fletcher, F. Dumur, M. M. Pollard, B. L. Feringa,
Science 2005, 310, 80.
4. Experimental Section
All the chemical reagents were purchased as high purity (AR grade)
and used without any further purification. The obtained salts for crystal
growth were verified by element analysis, X-ray powder diffraction
and FT-IR spectrum. FT-IR spectra were recorded on a Spectrum One
spectrophotometer (PerkinElmer) using KBr pallets. XRPD patterns
were recorded by an X-ray diffractometer (Rigaku Corporation SCXmini).
Elemental analyses for C, H, N and O contents were performed on the
Elementar Vario MICRO elemental analyzer. Anal. Calcd: H 4.93, C 52.57, N
7.21, O 12.36; found: H 4.89, C 52.60, N 7.20, O 12.33. Thermal stabilities
and specific heat were respectively measured by TGA using a Netzsch STA
449C unit, and DSC using a differential thermal analyzer of Netzsch DSC
200 F3 with the heating rate of 10 K/min. Dielectric experiments were
carried out on single-crystal specimen by TH2828 Precision LCR Meter.
The electrodes were made by sputtering silver onto both sides of samples
and attaching copper leads with silver paste. Calibration of standard
capacitor reveals that the experimental errors are within 3% accuracy.
Third-order NLO properties were investigated using a picosecond laser
(PY61C-10, Continuum, 532 nm at 28 ps) by the Z-scan technique.
All the crystal structures of 1 were measured on Rigaku CCD
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[11] Crystal data for complex 1 at 93 K (LTP): a = 17.500(12), b = 7.605(5),
diffractometer with Mokα radiation (λ
= 0.71073 Å) at various
temperatures. The CrystalClear software package (Rigaku, 2005) was
used for data collection, cell refinement and data reduction. Crystal
structures were solved by the direct methods and then refined by the
full-matrix method based on F2 using the SHELXTL software package
(Sheldrick, 2008). All non-hydrogen atoms were located from the trial
structure and refined anisotropically with SHELXTL using the full-
matrix least-squares procedure. The positions of hydrogen atoms were
generated geometrically and allowed to ride on the parent atoms.
c = 13.547(9) Å, β = 93.708(13)°, V = 1799(2) Å3, Z = 4, ρcalcd
=
1.434 g/cm3, R1(I >2σ(I)) = 0.0578, wR2(I >2σ(I)) = 0.1230, S =
1.145; 1 at 293 K (RTP): C17H19F3N2O3S, Mr = 388.40, Monoclinic,
P21/c, a = 17.508(5), b = 7.607(2), c = 13.533(4) Å, β = 93.712(6)°,
V = 1798.4(10) Å3, Z = 4, ρcalcd = 1.401 g/cm3, R1(I >2σ(I)) =
0.0575, wR2(I >2σ(I)) = 0.1687, S = 0.979; 1 at 338 K (ITP): a =
7.1842(14), b = 7.6856(17), c = 34.011(7) Å, β = 90.111(4)°, V =
1877.9(7) Å3, ρcalcd = 1.374 g/cm3, R1(I >2σ(I)) = 0.1085, wR2(I
>2σ(I)) = 0.3188, S = 1.102; 1 at 343 K (HTP): a = 7.190(9), b =
7.698(10), c = 34.08(4) Å, β = 90.05(4)°, V = 1886(4) Å3, Z = 4,
ρcalcd = 1.368 g/cm3, R1(I >2σ(I)) = 0.1027, wR2(I >2σ(I)) = 0.2304,
S = 0.838. CCDC 865587-865590 contain the supplementary crys-
tallographic data, which can be obtained free of charge from
Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/
data_request/cif.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by the NSFC (Nos. 51102231 and
21171166), the 973 Key Programs of the MOST (Nos. 2010CB933501 and
2011CB935904) the One Hundred Talent Program of Chinese Academy
of Sciences, and the Key Project of Fujian Province (2012H0045).
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Adv. Funct. Mater. 2012,
DOI: 10.1002/adfm.201201770
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