Magnetic properties of all-organic liquid crystals containing a chiral five-membered cyclic nitroxide unit within the rigid core

Article abstract of DOI:10.1002/anie.200460007

Lining them up: Purely organic paramagnetic liquid crystals (see picture) showing thermally stable nematic or cholesteric phases were successfully prepared. The molecular orientation of the bulk liquid crystals induced by weak magnetic fields was confirme

Full text of DOI:10.1002/anie.200460007

Angewandte
Chemie
advantage of a paramagnetic susceptibility anisotropy (Dcpara
for the orientation of LCs by weak magnetic fields, because
cpara is usually one or two orders of magnitude larger than cdia
)
.
For this reason, a number of metallomesogens with perma-
nent spins that originate from their transition-metal centers
have been prepared.[1,3] Particularly, calamitic lanthanide-
containing metallomesogens have a large paramagnetic
anisotropy, but the intrinsic high viscosity brought about by
the ligand-coordinated metal-complex structure frequently
renders their orientation by weak magnetic fields difficult.[3]
In contrast, a calamitic organic LC with a stable nitroxyl
(NO) group as a spin source can benefit from a small
paramagnetic susceptibility anisotropy and a low viscosity by
means of an appropriate molecular design; for example, 1) a
cyclic nitroxide framework is incorporated into the rigid core
of the mesogen to maximize the paramagnetic anisotropy, and
2) the side chains are extended from the two quaternary
carbon atoms adjacent to the nitroxyl group to reduce the
viscosity. Consequently, its orientation may be controlled by
weak magnetic fields.
Liquid Crystals
To test the above assumption, it is essential to find a
prototype of the calamitic mesogen that exhibits an extremely
stable paramagnetic liquid-crystalline phase. Furthermore, to
obtain a series of mesogens showing the nematic and chiral-
nematic (cholesteric) phases, and/or the smectic and chiral-
smectic phases,[4] the prototypic molecular structure should be
chiral. However, very few LCs containing the organic spin
center have been prepared mainly because the geometry and
bulkiness of the radical-stabilizing substituents are detrimen-
tal to the stability of liquid-crystalline phases. Their molecular
structures were limited to those containing a nitroxyl group
within the alkyl side chain, away from the rigid core and hence
allowed the free rotation of the nitroxyl moiety inside the
molecule, leading to a decrease in the paramagnetic aniso-
tropy of the whole molecule.[5] Unfortunately, all attempts to
prepare monomeric or polymeric mesogens by using the
organic spin as part of the rigid core have been unsuccess-
ful.[5,6]
With this in mind, we focused on the chiral 3,4-dihydro-
2,5-dimethyl-2H-pyrrole 1-oxide (1) from which a variety of
chiral derivatives can be prepared in the form of racemates or
nonracemates (Scheme 1).[7] First we synthesized the C2-
symmetric trans-2,5-bis(alkoxyphenyl) derivatives 2a–e with
various alkyl side chains, but they were not liquid-crystal-
line—this was most likely a result of their compact molecular
packing in the crystalline state as judged from the crystal
structures of (Æ )-2a and (2S,5S)-2a (Figure 1).[8] We then
modified the molecular structure to decrease the molecular
symmetry and strengthen the core-to-core interactions in the
liquid-crystalline state. Consequently, the C1-symmetric trans-
2-alkoxyphenyl-5-[4-(4-alkoxybenzenecarbonyloxy)phenyl]
derivatives 3, which have disordered alkyl side chains in the
crystalline state (Figure 2), successfully exhibited enantio-
tropic liquid-crystalline phases over wide temperature ranges
(see Table 1and Supporting Information); the racemic
samples of 3a–d showed a Schlieren texture typical for a
nematic phase by hot-stage polarizing microscopy (Fig-
ure 3a), whereas the corresponding nonracemic samples
(94–97% ee) exhibited an oily-streak texture characteristic
Magnetic Properties of All-Organic Liquid
Crystals Containing a Chiral Five-Membered
Cyclic Nitroxide Unit within the Rigid Core
Naohiko Ikuma, Rui Tamura,* Satoshi Shimono,
Naoyuki Kawame, Osamu Tamada, Naoko Sakai,
Jun Yamauchi, and Yukio Yamamoto
The orientation of liquid crystals (LCs) can generally be
controlled by magnetic and electric fields owing to their
molecular magnetic and dielectric anisotropies, respectively.
The threshold of the magnetic fields necessary to align liquid-
crystalline substances decreases with increasing magnetic
susceptibility anisotropy (j Dc j ) of the mesogens and the
decreasing viscosity of the material.[1] As the orientation of a
diamagnetic calamitic organic LC by external magnetic fields
is ascribed to the small diamagnetic susceptibility anisotropy
(0 < j Dcdia j < 60 ” 10À6 emumolÀ1) of the mesogen which
arises from the constituent aromatic rings,[2] relatively strong
magnetic fields (> 1T) are necessary for the orientation of
this type of LC. Therefore, it is quite reasonable to take
[*] N. Ikuma, Prof. R. Tamura
Graduate School of Global Environmental Studies and
Graduate School of Human and Environmental Studies
Kyoto University, Kyoto 606-8501 (Japan)
Fax : (+81)75-753-7915
E-mail: tamura@fischer.jinkan.kyoto-u.ac.jp
S. Shimono, N. Kawame, Prof. O. Tamada, N. Sakai,
Prof. Y. Yamamoto
Graduate School of Human and Environmental Studies
Kyoto University, Kyoto 606-8501 (Japan)
Prof. J. Yamauchi
Graduate School of Science, Kyoto University
Kyoto 606-8501 (Japan)
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
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DOI: 10.1002/anie.200460007
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Scheme 1. Preparation of chiral nitroxides 2 and 3. Reagents and con-
Figure 1. Crystal structures of a) (Æ)-2a and b) (2S,5S)-2a. The
carbon, nitrogen, and oxygen atoms are represented by open, grid, and
closed circles, respectively. Hydrogen atoms are omitted for clarity.
ditions: a) 1. R1MgBr, THF À788C; 2. Cu(OAc)2, O2; b) 1. R2MgBr,
À788C; 2. Cu(OAc)2, O2; c) TBAF, Et3N. CmH2m+1OC6H4COCl, THF,
08C. TBAF=tetra-n-butylammonium fluoride
of a cholesteric phase (Figure 3b).[4] These liquid-crystalline
phases are extremely thermally stable; for example, after
allowing (Æ )-3c to stand at 738C for 24 h, there was no
decrease in the purity of the material, and the racemic and
nonracemic samples of 3a–d did not decompose after several
heating and cooling cycles between the individual melting and
clearing points.
More interesting are the bulk magnetic properties of 3.
The magnetic susceptibilities of the racemic and nonracemic
samples of 3a–d were measured in a quartz tube (3.5 f”
40 mm) on a SQUID susceptometer at a field of 0.5 T in the
temperature range 2–380 K. During the first heating process
starting from the crystalline phase, (Æ )-3c and (Æ )-3d
Figure 2. Crystal structure of (2S,5S)-3a viewed down
the a axis. Both terminal butyl groups are disordered.
The carbon, nitrogen, and oxygen atoms are repre-
sented by open, grid, and closed circles, respectively.
Hydrogen atoms are omitted for clarity.
Table 1: Optical, magnetic, and thermal data of 3a–d.
ESR[b]
Compound
ee [%][a]
[a]2D6[b]
g
aN [mT]
C [emuÀ1 KmolÀ1 [c]
]
q [K][d]
Phase transition [8C][e]
(Æ)-3a
–
94.5
–
2.0068
2.0068
1.34
1.34
0.37[f]
À0.04[f]
C 113.2 N 140.6 I
C 93.2 N* 143.8 I
(2S,5S)-3a
À111.40
(c=0.993)
–
À95.59
(c=0.995)
–
À88.80
(c=0.998)
–
0.37[f], 0.38[g]
À0.01,[f] À0.40[g]
(Æ)-3b
–
94.9
2.0070
2.0069
1.33
1.34
0.38,[f] 0.38[g]
0.38,[f] 0.38[g]
À0.21,[f] À0.28[g]
C 67.1 N 103.4 I
C 67.6 N* 101.7 I
(2S,5S)-3b
À0.07,[f] À0.31 g]
(Æ)-3c
–
96.9
2.0073
2.0070
1.37
1.34
0.36,[f] 0.37[g]
0.37,[f] 0.37[g]
+0.38,[f] À0.40[g
À0.01,[f] À0.26[g]
C 63.3 N 103.1 I
C 79.3 N* 103.5 I
(2S,5S)-3c
(Æ)-3d
–
95.8
2.0069
2.0069
1.34
1.34
0.38,[f] 0.38[g]
0.38,[f] 0.38[g]
+0.31,[f] À0.34[g]
C 71.5 N 103.1I
C 71.2 N* 97.6 I
(2S,5S)-3d
À87.24
À0.10,[f] À0.33[g]
(c=0.981)
[a] Determined by HPLC analysis on a chiral stationary phase column (Daicel OD-H, 0.4”25 cm) and a mixture of hexane and 2-propanol (9:1) as the
mobile phase. [b] Measured in THF. [c] Curie constant. [d] Weiss temperature. [e] Determined by DSC analysis upon heating. Standard notation gives
the transition temperatures between the crystalline (C), liquid crystalline (N=nematic, N*=chiral nematic), and isotropic (I) states. [f] First heating
process from the crystalline phase. [g] First cooling process from the isotropic phase.
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showed weak ferromagnetic intermolecular interactions,
whereas the other samples showed weak antiferromagnetic
interactions. On the other hand, during the first cooling
process from the isotropic phase, all of the samples except
(Æ )-3a showed weak antiferromagnetic intermolecular inter-
actions (Figure 4 and Table 1).[9] Noteworthy is the distinct
change in the cpara values observed at the crystal-to-LC phase
transition during the first heating process; for example, (Æ )-
3c showed an abrupt increase in cpara at 342 K, followed by a
sudden decrease at 378 K (Figure 4c). But during the cooling
run from the isotropic phase, neither an appreciable decrease
in cpara nor the LC-to-crystal phase transition in the DSC
curve were observed, owing to the considerable stability of
the supercooled liquid-crystalline phase; the glassy phase was
preserved for more than 24 h at 258C.
In contrast, for (2S,5S)-3c of 96.9% ee, only a small
increase in cpara was noted upon the crystal-to-LC phase
transition during the first heating process (Figure 4d). Such
differences in the observed changes in cpara values between the
racemic and nonracemic samples can be accounted for by
their molecular arrangement in the nematic and cholesteric
phases, respectively; that is, the racemic nematic phase has
only orientational order along the long molecular axis,
whereas the nonracemic cholesteric phase has an additional
helical superstructure with a twist axis perpendicular to the
local director. The distinct increase in cpara upon the phase
change during the first heating process of (Æ )-3c is assumed
to originate from the orientation of the molecules in the
liquid-crystalline phase with the axis of maximum suscepti-
Figure 3. Optical polarized micrographs showing a) Schlieren texture
of (Æ)-3c at 93.08C and b) oily streaks texture of (2S,5S)-3c at 83.08C.
Figure 4. Temperature dependence of the magnetic susceptibility of a) (Æ)-3c and b) (2S,5S)-3c at the rate of 28CminÀ1 between 2 and 380 K at
a field of 0.5 T, c) (Æ)-3c and d) (2S,5S)-3c at the rate of 0.58CminÀ1 between 320 and 380 K at a field of 0.5 T, and (e) (Æ)-3c at the rate of
0.58CminÀ1 between 320 and 380 K at a field of 0.05 T, measured during the first heating and cooling processes. and represent the first heat-
~
*
~
*
ing process, and represent the first cooling process.
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bility parallel to the magnetic field. Such an increase in cpara
spectroscopy (Figures 5 and 6). During the heating process,
the g value of (Æ )-3c gradually decreased in the crystalline
state, then decreased abruptly upon the crystal-to-LC phase
transition, and then became constant in the liquid-crystalline
state. However, during the cooling process g was constant in
the liquid-crystalline state and then gradually increased in the
supercooled liquid-crystalline state (Figure 6a). As the g
value of a nitroxyl group generally shows distinct anisotropy
(in which the gxx value along the NO axis is 2.008–2.009, the
gzz value along its 2pz orbital axis is less than 2.003, and the gyy
value perpendicular to both axes is 2.005–2.006[10]), the
observed decrease in g from 2.0065 to 2.0052 is assumed to
correspond to the increasing contribution of the gyy and gzz
values; that is, the majority of the molecules align in such a
way that the NO axis is perpendicular to the applied magnetic
field (Scheme 2). Accordingly, on the basis of the molecular
structure of 3a (Figure 2), the molecular long axis as well as
the director axis should be approximately oriented parallel to
the direction of the magnetic field. In contrast, for (2S,5S)-3c,
g did not show any temperature dependence, and the value
was almost constant between 2.0060 and 2.0070, close to the
mean value in solution (Figure 6b); this result seems to reflect
the peculiar helical superstructure of the cholesteric phase in
which a uniform molecular orientation is impossible.[4]
upon the crystal-to-LC phase transition was also observed at a
field of 0.05 T or below (Figure 4e). This is a rare example in
which the orientation of the mesogens can be effected by very
weak magnetic fields during the heating process.[1,2]
To gain better insight into the direction of the molecular
orientation in the bulk LC in the magnetic field, the temper-
ature dependence of the g value for 3c was measured by EPR
Figure 5. Selected EPR spectra of (Æ)-3c measured at various temper-
atures from the crystalline phase (top) through the liquid-crystalline
phase to the supercooled liquid-crystalline phase (bottom).
Furthermore, a striking increase in the intensity of the
EPR signal was observed for both racemic and nonracemic
Figure 6. Variation of the g values of a) (Æ)-3c and b) (2S,5S)-3c, and the signal intensities of c) (Æ)-3c and d) (2S,5S)-3c, upon variation of the
*
*
temperature; measured through the first heating ( ) and cooling ( ) processes.
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[3] a) K. Binnemans, Y. G. Galyametdinov, R. V. Deun, D. W.
samples of 3c upon the phase transition
observed during the heating process
from the crystalline phase (Figures 6c
and d). During the cooling process from
the isotropic phase, the intensity grad-
ually increased in the liquid-crystalline
and the supercooled liquid-crystalline
phases in both samples. In line with the
intensity of the EPR signal being pro-
portional to the c value, a microscopic
increase in the cpara value was indeed
observed upon the phase transition
from the crystalline phase to the nem-
atic or cholesteric phase.
Bruce, S. R. Collinson, A. P. Polishchuk, I. Bikchantaev, W.
Haase, A. V. Prosvirin, L. Tinchurina, I. Litvinov, A. Gubajdul-
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Chem. Soc. 2000, 122, 4335 – 4344; b) Y. Galyametdinov, M. A.
Athanassopoulou, K. Griesar, O. Kharitonova, E. A. S. Busta-
mante, L. Tinchurina, I. Ovchinnikov, W. Haase, Chem. Mater.
1996, 8, 922 – 926; c) K. Griesar, Y. Galyametdinov, M. Atha-
nassopoulou, I. Ovchinnikov, W. Haase, Adv. Mater. 1994, 6,
381– 384.
[4] a) I. Dierking, Texture of Liquid Crystals, Wiley-VCH, Wein-
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Liquid Crystals, Wiley-VCH, Weinheim, 999; c) D. Demus, J. W.
Goodby, G. W. Gray, H. W. Spiess, V. Vill, Handbook of Liquid
Crystals, Vol. 1–4, Wiley-VCH, Weinheim, 1998.
[5] a) S. Nakatsuji, M. Mizumoto, H. Ikemoto, H. Akutsu, J.
Yamada, Eur. J. Org. Chem. 2002, 1912 – 1918; b) J. Allgaier,
H. Finkelmann, Macromol. Chem. Phys. 1994, 195, 1017 – 1030;
c) M. Dvolaitzky, J. Billard, F. Poldy, Tetrahedron 1976, 32, 1835 –
1838; d) M. Dvolaitzky, J. Billard, F. Poldy, C. R. Hebd. Seances
Acad. Sci. Ser. C 1974, 279, 533 – 535.
[6] a) S. Shimono, R. Tamura, N. Ikuma, T. Takimoto, N. Kawame,
O. Tamada, N. Sakai, H. Matsuura, J. Yamauchi, J. Org. Chem.
2004, 69, 475 – 481; b) R. Tamura, S. Shimono, K. Fujita, K.
Hirao, Heterocycles 2001, 54, 217 – 224; c) R. Tamura, S. Susuki,
N. Azuma, A. Matsumoto, F. Toda, T. Takui, D. Shiomi, K. Itoh,
Mol. Cryst. Liq. Cryst. 1995, 271, 91– 96; d) R. Tamura, S.
Susuki, N. Azuma, A. Matsumoto, F. Toda, Y. Ishii, J. Org. Chem.
1995, 60, 6820 – 6825; e) R. Tamura, S. Susuki, N. Azuma, A.
Matsumoto, F. Toda, A. Kamimura, K. Hori, Angew. Chem.
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[7] a) N. Ikuma, R. Tamura, S. Shimono, N. Kawame, O. Tamada, N.
Sakai, J. Yamauchi, Y. Yamamoto, Mendeleev Commun. 2003,
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Scheme 2. Molecular
orientation of 3
approximately paral-
lel to the magnetic
field (H0).
We thus observed the microscopic
decrease in the g value as well as the
macro- and microscopic increases in the
cpara value upon the phase transition
from the crystalline phase of (Æ )-3c to
the liquid-crystalline phase during the heating process.
It is assumed that the molecular magnetic susceptibility
anisotropy (Dc), which results from the cooperation of the
paramagnetic and diamagnetic components originating from
the nitroxyl group and the benzene rings, respectively, is
responsible for the orientation of the bulk LC in the applied
magnetic field. As c (parallel) is surely larger than c
k
?
(perpendicular) for (Æ )-3c, the experimental magnetic sus-
ceptibility anisotropy Dcexp was determined to be + 0.47 ”
10À4 emumolÀ1 according to Equation (1),[2a] in which the
3
2
ð1Þ
Dcexp
¼
ðcorderedÀcisotropic
Þ
experimental values of cordered = + 1.136 ” 10À3 emumolÀ1 at
340 K (cooling process) and cisotropic = + 1.105 ”
10À3 emumolÀ1 at 340 K (heating process) were used.
Thus, it has been shown that a chiral racemic nematic
phase is more suitable than a cholesteric phase with respect to
the orientation of the bulk LC by weak magnetic fields.
Alternatively, these paramagnetic LC substances may serve as
dopants to align diamagnetic mesophases by weak magnetic
fields, or as a real LC probe to investigate the dynamic
behavior of a given diamagnetic LC material by EPR
spectroscopy. Furthermore, if a paramagnetic chiral smectic
(SmC*) phase is available, the orientation of the ferroelectric
sample may also be controlled by application of weak
magnetic fields.[11]
[8] The X-ray crystallographic data were collected at 298 K on an
Enraf-Nonius Kappa CCD diffractometer. The crystal structure
was solved by direct methods and refined by full-matrix least
squares. All non-hydrogen atoms were refined anisotropically.
All of the crystallographic calculations were performed by using
the maXus software package.[12] Crystal data for (Æ )-2a:
C26H36NO3, Mr = 410.578, 0.26 ” 0.20 ” 0.16 mm3, monoclinic,
space group C2/c, a = 14.363(2), b = 15.1763(13), c =
22.269(4) Š, b = 99.155(7)8, V= 4792.5(12) Š3, Z = 8, 1calcd
=
1.138 gcmÀ3
,
2qmax = 50.728, MoKa (l = 0.71073 Š), m =
0.73 cmÀ1, f-w-scans, T= 298 K, 4403 independent reflections,
2133 observed reflections (I > 2.0s(I)), 295 refined parameters,
À3
R = 0.064, Rw = 0.166, D1max = 0.320 eŠÀ3, D1min = À0.341eŠ
.
Crystal data for (2S,5S)-2a: C26H36NO3, Mr = 410.578, 0.31 ”
0.21” 0.09 mm , triclinic, space group P1, a = 6.3786(2), b =
Received: March 16, 2004 [Z460007]
3
¯
7.5419(3), c = 13.7089(9) Š, a = 98.448(2)8, b = 90.959(2)8, g =
Keywords: chirality · EPR spectroscopy · liquid crystals ·
magnetic properties · phase transitions
114.567(4)8, V= 591.06(5) Š3, Z = 1, 1calcd = 1.154 gcmÀ3, 2qmax
=
.
54.968, MoKa(l = 0.71073 Š), m = 0.74 cmÀ1
, f-w-scans, T=
298 K, 2611 independent reflections, 1396 observed reflections
(I > 2.0s(I)), 277 refined parameters, R = 0.058, Rw = 0.119,
À3
À3
D1max = 0.215 eŠ
,
D1min = À0.258 eŠ
. Crystal data for
[1] a) K. Griesar, W. Haase in Magnetic Properties of Organic
Molecules (Ed.: P. M. Lahti), Marcel Dekker, New York, 1999,
pp. 325 – 344; b) P. Kaszynski in Magnetic Properties of Organic
Molecules (Ed.: P. M. Lahti), Marcel Dekker, New York, 1999,
pp. 305 – 324; c) M. Marcos, J.-L Serrano, Adv. Mater. 1991, 3,
256 – 257.
(2S,5S)-3a: C33H40NO5, Mr = 530.685, 0.36 ” 0.30 ” 0.03 mm3,
monoclinic, space group P21, a = 7.1625(7), b = 9.696(2), c =
21.609(2) Š, b = 98.171(6)8, V= 1485.5(4) Š3, Z = 2, 1calcd
=
m =
1.186 gcmÀ3
,
2qmax = 49.808,
MoKa(l = 0.71073 Š),
0.79 cmÀ1, f-w-scans, T= 298 K, 2733 independent reflections,
1809 observed reflections (I > 2.0s(I)), 424 refined parameters,
[2] H. Müller, W. Haase, J. Phys. (Paris) 1983, 44, 1209 – 1213.
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À3
R = 0.048, Rw = 0.091, D1max = 0.191 eŠÀ3, D1min = À0.201eŠ
.
CCDC-233749–233751contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from
the Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB21EZ, UK; fax: (+ 44)1223-336-033; or deposit@
ccdc.cam.ac.uk).
[9] For recent reviews, see: a) Magnetism: Molecules to Materials II
(Ed.: J. S. Miller, M. Drillon), Wiley-VCH, Weinheim, 2001;
b) S. Nakatsuji, H. Anzai, J. Mater. Chem. 1997, 7, 2161 – 2174
c) J. Veciana, J. Cirujeda, C. Rovira, J. Vidal-Gancedo, Adv.
Mater. 1995, 7, 221– 225. Also see ref [1].
[10] a) O. Takizawa, J. Yamauchi, H. O. Nishiguchi, Y. Deguchi, Bull.
Chem. Soc. Jpn. 1973, 46, 1991 – 1995; b) O. H. Griffith, D. W.
Cornell, H. M. McConnell, J. Chem. Phys. 1965, 43, 2909 – 2910.
[11] T. Kimura, T. Goto, H. Shintani, K. Ishizaka, T. Arima, Y.
Tokura, Nature 2003, 426, 55 – 58.
[12] S. Mackay, C. J. Gilmore, C. Edwards, M. Tremayne, N. Stuart, K.
Shankland, maXus: A Computer Program for the Solution and
Refinement of Crystal Structures from Diffraction Data, Univer-
sity of Glasgow, Scotland, UK, Nonius BV, Delft, The Nether-
lands and MacScience Co. Ltd., Yokohama, Japan, 1998.
[13] The Supporting Information contains Figure S1, in which the
DSC curves and temperature-variable XRD patterns of (Æ )-3c
and (2S,5S)-3c are shown.
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