Nonclassical tunability of solid-state CD and CPL properties of a chiral 2-naphthalenecarboxylic acid/amine supramolecular organic fluorophore

Article abstract of DOI:10.1002/asia.201100727

The solid-state chiral optical properties (circular dichroism and circularly polarized luminescence) of a 2-naphthalenecarboxylic acid/amine supramolecular organic fluorophore can be controlled by changing the aryl unit of the chiral 1-arylethylamine component of the molecule rather than altering the chirality of the 1-arylethylamine itself. Predisposed to glow: The solid-state circular dichroism and circularly polarized luminescence of a 2-naphthalenecarboxylic acid/amine supramolecular organic fluorophore can be controlled by changing the aryl unit of the chiral 1-arylethylamine component rather than changing the chirality of the 1-arylethylamine itself (see picture).

Full text of DOI:10.1002/asia.201100727

FULL PAPERS
DOI: 10.1002/asia.201100727
Nonclassical Tunability of Solid-State CD and CPL Properties of a Chiral 2-
Naphthalenecarboxylic Acid/Amine Supramolecular Organic Fluorophore**
Noriaki Nishiguchi,[a] Takafumi Kinuta,[a] Tomohiro Sato,[a] Yoko Nakano,[b]
Hayato Tokutome,[c] Nobuo Tajima,[d] Michiya Fujiki,[b] Reiko Kuroda,[c]
Yoshio Matsubara,[a] and Yoshitane Imai*[a]
Abstract: The solid-state chiral optical properties (circular dichroism and circularly
polarized luminescence) of a 2-naphthalenecarboxylic acid/amine supramolecular
organic fluorophore can be controlled by changing the aryl unit of the chiral 1-ary-
lethylamine component of the molecule rather than altering the chirality of the 1-
arylethylamine itself.
Keywords: chirality · crystal engi-
neering · fluorescence · lumines-
cence · supramolecular chemistry
Introduction
lar dichroism (CD) and circularly polarized luminescence
(CPL).
Solid-state organic fluorophores have attracted considerable
attention in the field of optoelectronics for application in
devices such as organic electroluminescence (EL) devices
and optical sensors.[1] Recently, two or more component
solid-state supramolecular organic fluorophores have gained
considerable interest because their optical properties can be
easily controlled by changing the component molecules
without synthetic processes.[2] On the other hand, most of
the previously reported supramolecular organic fluoro-
phores or organic fluorophores composed of a single organic
molecule were not chiral, and therefore, did not display
solid-state chiral optical properties such as solid-state circu-
Typically, to control the sign of the optical properties of a
given chiral compound, a chiral compound with the opposite
chirality is used. However, chiral compounds with opposite
chirality may not be easily available. Therefore, it is desira-
ble to develop a way of tuning the sign of the optical proper-
ties of a chiral fluorophore without using an opposite-chiral-
ity counterpart in the development of new chiral fluorescent
systems.
Herein, we report the nonclassical tunability of the solid-
state chiral optical properties of a new chiral two-compo-
nent supramolecular organic fluorophore. The solid-state
chiral optical properties of a 2-naphthalenecarboxylic acid/
1-arylethylamine supramolecular organic fluorophore are
tunable by changing the type of aryl unit in the chiral 1-ary-
lethylamine component molecule, but not the chirality of
the 1-arylethylamine itself. In this system, 2-naphthalenecar-
boxylic acid (1) was used as the fluorescent component mol-
ecule. Three types of chiral 1-arylethylamines, (R)-(+)-1-
phenylethylamine ((R)-2), (R)-(+)-1-(p-tolyl)ethylamine
((R)-3), and (R)-(+)-1-(4-methoxyphenyl)ethylamine ((R)-
4), possessing different aryl units, but the same chirality,
were used as the chiral (R)-(+)-1-arylethylamine component
molecule.
[a] N. Nishiguchi, T. Kinuta, T. Sato, Prof. Dr. Y. Matsubara, Dr. Y. Imai
Department of Applied Chemistry
Faculty of Science and Engineering
Kinki University
3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502 (Japan)
Fax : (+81)6-6727-2024
E-mail: y-imai@apch.kindai.ac.jp
[b] Dr. Y. Nakano, Prof. Dr. M. Fujiki
Graduate School of Materials Science
Nara Institute of School and Technology
Takayama, Ikoma, Nara 630-0192 (Japan)
[c] H. Tokutome, Prof. Dr. R. Kuroda
Department of Life Sciences
Graduate School of Arts and Sciences
The University of Tokyo
3-8-1 Komaba, Meguro-ku, Tokyo 153-8902 (Japan)
[d] Dr. N. Tajima
Computational Materials Science Center
National Institute for Materials Science
1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan)
[**] CD=circular dichroism, CPL=circularly polarized luminescence.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201100727.
360
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 360 – 366

Results and Discussion
The three versions of the chiral supramolecular organic fluo-
rophore, 1/(R)-2–4, were prepared by crystallization from a
solution containing 1 and (R)-2–4 in MeOH. Compounds 1
and (R)-2 (or (R)-3 or (R)-4) were dissolved in MeOH and
left to stand at room temperature. After one week, a large
number of crystals of complexes I (composed of 1 and (R)-
2), II (composed of 1 and (R)-3), and III (composed of 1
and (R)-4) were obtained.
The most serious problem associated with solid-state fluo-
rophores is the occurrence of fluorescence quenching in the
crystalline state. To study the solid-state optical properties
of complexes I–III, we first measured solid-state fluores-
cence spectra. The crystal form and solid-state fluorescence
spectral data of complexes I–III are presented in Table 1.
Table 1. Crystal form and solid-state fluorescence spectral data of com-
plexes I–III.
Complex
Crystal color
Crystal shape
lem [nm][a]
FF
I
II
III
colorless
colorless
colorless
Plate
Needle
Needle
349
348
348
0.09
0.12
0.08
[a] Excited wavelengths are 329, 330, and 327 nm for complexes I–III, re-
spectively.
Complexes I–III all exhibit fluorescence in the solid state.
The solid-state fluorescence maximum (lem) for complex I is
observed at 349 nm and the absolute value of the photolu-
minescence quantum yield (FF) for complex I is 0.09 in the
solid state. The solid-state lem and FF values for complexes
I–III are similar, despite the use of 1-arylethylamine mole-
cules with different aryl units.
To study the trends in the solid-state chiral optical proper-
ties (CD and CPL) of the 2-naphthalenecarboxylic acid/1-ar-
ylethylamine supramolecular organic fluorophore, the solid-
state CD spectra of fluorescent complexes I–III were mea-
sured as KBr pellets. The solid-state CD and absorption
spectra of complexes I–III (indicated by black lines) are
shown in Figure 1. The shapes of these CD spectra are simi-
lar. Characteristic peaks of the naphthalene unit are ob-
served between 260 and 350 nm. The circular anisotropy fac-
tors (jgCD =DOD/ODj ; OD=optical density) of the last
Cotton effect (lCD =330 nm for I, 333 nm for II, and 329 nm
Abstract in Japanese:
Figure 1. CD and absorption spectra of complexes a) I, b) II, and c) III
(black lines) and complexes I’–III’ (gray lines) in the solid state (as KBr
pellets).
for III) for I, II, and III are approximately 5.6ꢁ10ꢀ4, 7.2ꢁ
10ꢀ4, and 3.7ꢁ10ꢀ4, respectively.
Chem. Asian J. 2012, 7, 360 – 366
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
361

Y. Imai et al.
FULL PAPERS
To check whether complexes I–III introduced any artifact
into the spectra, complexes I’–III’ were prepared, in which
compounds (R)-2–4 were replaced with (S)-(ꢀ)-1-phenyle-
thylamine ((S)-2), (S)-(ꢀ)-1-(p-tolyl)ethylamine ((S)-3), and
(S)-(ꢀ)-1-(4-methoxyphenyl)ethylamine ((S)-4). Then, the
solid-state CD spectra of complexes I’–III’ were measured
(indicated by gray lines in Figure 1). These CD spectra were
mirror images of the CD spectra of complexes I–III. These
results indicate that effective chiral transfer occurs from
chiral compounds 2–4 to complexes I–III through complexa-
tion.
Interestingly, although chiral complexes I–III (or I’–III’)
are composed of amine component molecules with the same
chirality, the signs of the CD spectra of chiral complexes I–
III (or I’–III’) are not all the same. That is, the signs of the
CD spectra of complexes I and II at the longest wavelengths
are negative (indicated by black lines in Figure 1a and b),
whereas that of complex III is positive (indicated by black
lines in Figure 1c). This shows that the solid-state CD prop-
erty of the 2-naphthalenecarboxylic acid/1-arylethylamine
supramolecular organic fluorophore can be controlled by
changing the aryl unit in the chiral 1-arylethylamine compo-
nent to another aryl unit with the same chirality.
To study the origin of the solid-state CD properties of
these complexes, X-ray crystallographic analyses of com-
plexes I–III were conducted and the resulting crystal struc-
tures of complexes I–III were compared. The crystal struc-
tures of I are shown in Figure 2.[3] The stoichiometry of com-
plex I is 1:1 with regards to the components 1/(R)-2 and the
complex is in the space group P212121. This complex has a
characteristic 21-helical columnar network structure along
the a axis (Figure 2a and b). This column is mainly com-
posed of the carboxylate oxygen atoms of the carboxylic
acid anions and the ammonium hydrogen atoms of the pro-
tonated amine. Complex I is formed by the assembly of
these 21-helical columns (indicated by the dotted circle in
Figure 2c) without major intercolumnar interactions (Fig-
ure 2c).[4]
The crystal structures of II are shown in Figure 3. The sto-
ichiometry of II is 1:1 with regards to the components 1/(R)-
3 and the complex is in space group P212121, which is the
same as that of complex I. This complex also has a 21-helical
columnar network structure along the a axis similar to that
in complex I (Figure 3a). Complex II is formed by the as-
sembly of these 21-helical columns (indicated by the dotted
circle in Figure 3b) through three types of intercolumnar in-
teractions (Figure 3b):[4] 1) naphthalene–benzene edge-to-
face interactions (2.80 ꢂ, as indicated by arrow A in Fig-
ure 3b) between the hydrogen atom of the naphthalene ring
in 1 and the benzene ring of (R)-3; 2) benzene–naphthalene
edge-to-face interactions (2.95 ꢂ, as indicated by arrow B in
Figure 3b) between the hydrogen atom of the benzene ring
of (R)-3 and the naphthalene ring in 1; and 3) naphthalene–
naphthalene edge-to-face interactions between naphthalene
rings in 1 (2.83 ꢂ, as indicated by arrow C in Figure 3b). In-
terestingly, X-ray crystallography revealed that, although
the structures of the 21-helical columns in complexes I and
Figure 2. Crystal structures of I. a) 21-Helical columnar network structure
observed along the a axis. b) View along the c axis. c) Packing structure
observed along the a axis. The dotted circle represents a 21-helical colum-
nar network structure.
II are the same, the packing structures of the shared 21-heli-
cal columns are considerably different (cf. Figures 2c and
3b).
The crystal structures of III are shown in Figure 4. The
stoichiometry of III is 1:1 with regards to the components 1/
(R)-4 and the complex is in space group P1. In contrast to
complexes I and II, the component molecules 1 and (R)-4
form a pseudo-21-helical columnar network structure along
the a axis (Figure 4a). This column is also mainly composed
of the carboxylate oxygen atoms of the carboxylic acid
anions and the ammonium hydrogen atoms of the protonat-
ed amine. As expected, the packing structure of this pseudo-
21-helical column in complex III is also different from that
of complexes I and II. In III, there are three types of inter-
columnar interactions (Figure 4b):[4] 1) CH–p interactions
362
www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 360 – 366

Supramolecular Organic Fluorophore
Figure 4. Crystal structures of III. a) Pseudo-21-helical columnar network
structure along the a axis. b) Packing structure observed along the a axis.
Figure 3. Crystal structures of II. a) 21-Helical columnar network struc-
ture along the a axis. b) Packing structure observed along the a axis. The
dotted circle represents a 21-helical columnar network structure. Arrows
A, B, and C indicate the intercolumnar naphthalene–benzene, benzene–
naphthalene, and naphthalene–naphthalene edge-to-face interactions, re-
spectively.
The dotted circle represents
a helical columnar network structure.
Arrows A and B indicate the intercolumnar CH–p interactions. Arrows
C (or D) and E indicate the intercolumnar naphthalene–benzene and
benzene–naphthalene edge-to-face interactions, respectively.
the three crystals, in which the rotational strengths at 230–
250 nm correspond to the experimentally observed strong
CD intensities at 220–240 nm, whereas those at 300–350 nm
correspond to the CD intensities in the longest wavelength
region 260–300 nm we have focused on. Although the corre-
lation to the experimentally observed spectra is not good,
the calculated rotational strengths at 300–350 nm reproduce
the main features of the CD intensities at 260–300 nm ob-
served for the complexes. That is, we find a negative intensi-
ty of I (Figure 5a) and a positive intensity of III (Figure 5c),
although the intensity of II is barely observed (Figure 5b).
Complex III also has negative intensities (Figure 5d), but
the positive contribution overwhelms the negative one upon
summation. These rotational strengths result mainly from
between the methyl group in (R)-4 and the naphthalene ring
in 1 (2.58 and 2.55 ꢂ, as indicated by arrows A and B in Fig-
ure 4b, respectively); 2) naphthalene–benzene edge-to-face
interactions (2.71 and 2.89 ꢂ, as indicated by arrows C and
D in Figure 4b, respectively) between the hydrogen atom of
the naphthalene ring of 1 and the benzene ring in (R)-4;
and 3) benzene–naphthalene edge-to-face interactions be-
tween the hydrogen atom of the benzene ring of (R)-4 and
the naphthalene ring in 1 (2.94 ꢂ, as indicated by arrow E
in Figure 4b).
Complexes I and II have negative CD intensities at 260–
350 nm, which originate from the electronic absorption of
molecule 1, whereas complex III has a positive CD intensity
in the 260–350 nm region. The origins of the chiroptical
properties of complexes I–III were studied on the basis of
the X-ray structures. As described earlier, we focused on the
CD intensities in the longest wavelength region, 260–
350 nm, because not all three complexes have the same sign
despite having component amine molecules with the same
chirality. The weak electronic absorption in this wavelength
region, apparently originating from component molecule 1,
suggests that the corresponding CD intensities are induced
by molecular structure fixation of 1 in crystals. To verify this
hypothesis, the chiroptical properties of single molecules of
1 in the three complexes were examined theoretically.
Figure 5 displays the calculated rotational strengths for 1 in
ꢀ
ꢀ
distortions of 1 around the C CO2 bond: the OC CC dihe-
dral angles are ꢀ18.6 (ꢀ15.7) in I, 3.9 (3.3) in II, and 34.9
(34.4) and ꢀ42.08 (ꢀ38.98) in III. These calculated data sug-
gest that the molecular structure fixation of 1 possibly con-
tributes to the experimentally observed CD intensities in
the 260–350 nm region.
Next, the solid-state CPL spectra of complexes I–III were
measured as KBr pellets and compared. The solid-state CPL
and fluorescence spectra of complexes I–III are shown in
Figure 6.
The fluorescence spectra of these complexes measured as
KBr pellets are similar to those of complexes obtained with-
out using the KBr matrix. This result shows that the KBr
Chem. Asian J. 2012, 7, 360 – 366
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
363

Y. Imai et al.
FULL PAPERS
orophores offering these func-
tionalities are expected to be
useful in the development of
new solid-state chiral supra-
molecular fluorophores.
Experimental Section
General Methods
Component molecule
1 and MeOH
were purchased from Wako Pure
Chemical Industries. Component mol-
ecules (R)-2–4 and (S)-2–4 were pur-
chased from Tokyo Kasei Kogyo.
MeOH was used directly without fur-
ther purification.
Formation of Complexes I–III by
Crystallization from MeOH
Compounds
1
(11.5 mg,
6.68ꢁ
Figure 5. Calculated rotational strengths (in 10–40 ergesucmGaussꢀ1) and electronic excitation wavelength for
molecule 1: a) and b) molecules taking the geometries in I and II, respectively; c) and d) molecules taking the
geometries in III (two crystallographically independent molecules).
10ꢀ5 mol) and (R)-2 (or (R)-3, (R)-4;
6.68ꢁ10ꢀ5 mol) were dissolved in
MeOH (2 mL). After one week,
large number of crystals (crystals of
complexes (9 mg) for the 1/(R)-2
system, II (10 mg) for the 1/(R)-3
a
I
matrix does not introduce any artifacts into measurements
system, and III (10 mg) for the 1/(R)-4 system) were obtained. The mass
of the crystals was equal to the total mass of the crystals of complexes I,
II, and III obtained in one batch.
of the spectra. As expected, a comparison of the CPL prop-
erties of chiral complexes I–III indicates that the sign of the
CPL spectra changes from negative for I and II to positive
Theoretical Calculations
for
III.
The
circular
anisotropy
factor
(gem =
2
G
E
The excitation energies and rotational strengths of 1 were calculated by
the Zernerꢃs intermediate neglect of differential overlap (ZINDO)
method[5] from the molecular geometries in the complexes. In these cal-
culations, the deprotonated form of 1 was used instead of the neutral
form because the carbonate proton of 1 was transferred to the amine
molecule in complexes I–III. These quantum chemical calculations were
carried out by using the Gaussian 03 program.[6]
10ꢀ4, ꢀ2.5ꢁ10ꢀ4, and 7.6ꢁ10ꢀ4, respectively. To the best of
our knowledge, this is the first time that the sign of solid-
state CD and CPL spectra in a chiral supramolecular organ-
ic fluorophore composed of 1-arylethylamine has been con-
trolled by changing the type of aryl unit in the chiral 1-aryle-
thylamine component molecule without changing its chirali-
ty.
Measurement of Solid-State Fluorescence Spectra
The solid-state fluorescence spectra and absolute photoluminescence
quantum yields were measured by using the Absolute PL Quantum Yield
Measurement System (C9920-02, HAMAMATSU PHOTONICS K. K.)
in air at room temperature. The excitation wavelengths were 329, 330,
and 327 nm for complexes I, II, and III, respectively.
Conclusions
A chiral supramolecular organic fluorophore was successful-
ly prepared by forming a complex between achiral fluores-
cent 2-naphthalenecarboxylic acid and chiral (R)-(+)-1-ary-
lethylamines. By changing the aryl unit in the chiral (R)-
(+)-1-arylethylamine, the style of helical columnar network
structure and its packing arrangement was changed. As a
result, the signs of the solid-state CD and CPL spectra of
these supramolecular fluorophores could be reversed despite
using chiral amine component molecules with the same chir-
ality. These results show that the solid-state chiral optical
properties of the 2-naphthalenecarboxylic acid/amine supra-
molecular organic fluorophore can be controlled by replac-
ing the aryl unit in the chiral 1-arylethylamine component
molecule with another of the same chirality (that is, by
changing the style of helical column and its packing struc-
ture), instead of changing the chirality of the amine compo-
nent molecule in the solid state. Supramolecular organic flu-
Measurement of Solid-State CD and Absorption Spectra
The solid-state CD and absorption spectra were measured by using a
Jasco J-800 KCM spectrophotometer. The solid-state samples were pre-
pared according to standard procedures for obtaining glassy KBr matri-
ces.[7]
X-ray Crystallographic Study of Complexes I–III
X-ray diffraction data for single crystals were collected by using
a
BRUKER APEX diffractometer. The crystal structures were solved by a
direct method[8] and refined by full-matrix least-squares using the
SHELXL97 program.[8] Diagrams were prepared by using the PLATON
program.[9] Absorption corrections were performed by using the
SADABS program.[10] Non-hydrogen atoms were refined with anisotropic
displacement parameters and hydrogen atoms were included in the
models in their calculated positions in the riding model approximation.
Crystallographic data for I: C8H11N·C11H8O2; M=293.35; space group
P212121;
1592.2(2) ꢂ3; 1cald =1.224 gcmꢀ3; z=4; m
flections measured; 3648 unique: final R(F2)=0.0437 using 3194 reflec-
a=6.3454(5),
b=14.4425(11),
c=17.3736(13) ꢂ;
V=
AHCTUNGTRENNUNG
364
www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 360 – 366

Supramolecular Organic Fluorophore
Crystallographic data for II: C9H13N·C11H8O2; M=307.38; space group
P212121; a=6.0380(7), b=16.4105(18), c=16.7204(18) ꢂ; V=
1656.8(3) ꢂ3; 1cald =1.232 gcmꢀ3; z=4; m(MoKa)=0.079 mmꢀ1; 10358 re-
flections measured; 3774 unique; final R(F2)=0.0577 using 3026 reflec-
tions with I>2.0s(I); R(all data)=0.0758; T=115(2) K. CCDC 822730
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallograph-
ic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Crystallographic data for III: C9H13NO·C11H8O2; M=646.76; space group
P1; a=6.1134(7), b=7.2271(8), c=18.892(2) ꢂ; a=88.533(2), b=
88.910(2), g=88.428(2)8; V=833.94(16) ꢂ3; 1cald =1.288 gcmꢀ3; z=1; m-
A
;
7302 reflections measured; 5935 unique; final
R(F2)=0.0545 using 4641 reflections with I>2.0s(I);
RACHTUNGTRENNUG
0.0740; T=115(2) K. CCDC 822731 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.cam.a-
c.uk/data_request/cif.
Measurement of Solid-State CPL Spectra
The solid-state CPL spectra were measured by using a Jasco CPL-200
spectrophotometer. The excitation wavelengths were 329, 330, and
326 nm for complexes I–III, respectively. The solid-state samples were
prepared according to standard procedures for obtaining glassy KBr ma-
trices. The power of the incident beam of the CPL spectrometer was
0.3 mWcmꢀ2 at the installation position of sample. The CPL spectrum is
approached by Simple Moving Average (SMA).
Acknowledgements
This study was supported by a Grant-in-Aid for Scientific Research (nos.
22750133 and 23111720) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan, and a research grant from the TEPCO
Research Foundation.
[1] a) J. Shinar, Organic Light-Emitting Devices, Springer, Heidelberg,
2004; b) K. Mꢄllen, U. Scherf, Organic Light-Emitting Devices,
Wiley-VCH, Weinheim, 2006; c) C. Jeanne, R. Regis, Dalton Trans.
2008, 6865–6876; d) S. Kappaun, C. Slugovc, J. M. Emil, Int. J. Mol.
Sci. 2008, 9, 1527–1547; e) K. Milan, O. Franc, Acc. Chem. Res.
2009, 42, 235–248; f) W.-Y. Wong, C.-L. Ho, J. Mater. Chem. 2009,
19, 4457–4482; g) K.-L. Chan, P. Sonar, A. Sellinge, J. Mater. Chem.
2009, 19, 9103–9120; h) F. Laquai, Y.-S. Park, J.-J. Kim, T. Basche,
Macromol. Rapid Commun. 2009, 30, 1203–1231; i) C. Wang, J.
Zhang, K. Ryu, A. Badmaev, L. G. D. Arco, C. Zhou, Nano Lett.
2009, 9, 4285–4291; j) M.-K. Wei, C.-W. Lin, C.-C. Yang, Y.-W.
Kiang, J.-H. Lee, H.-Y. Lin, Int. J. Mol. Sci. 2010, 11, 1527–1545,
and references cited therein.
[2] a) Y. Mizobe, N. Tohnai, M. Miyata, Y. Hasegawa, Chem. Commun.
2005, 1839–1841; b) S. Oshita, A. Matsumoto, Langmuir 2006, 22,
1943–1945; c) Y. Mizobe, M. Miyata, I. Hisaki, Y. Hasegawa, N.
Tohnai, Org. Lett. 2006, 8, 4295–4298; d) Y. Imai, K. Kawaguchi, T.
Harada, T. Sato, M. Ishikawa, M. Fujiki, R. Kuroda, Y. Matsubara,
Tetrahedron Lett. 2007, 48, 2927–2930; e) Y. Imai, K. Murata, K.
Kawaguchi, T. Sato, R. Kuroda, Y. Matsubara, Org. Lett. 2007, 9,
3457–3460; f) Y. Mizobe, T. Hinoue, M. Miyata, I. Hisaki, Y. Hase-
gawa, N. Tohnai, Bull. Chem. Soc. Jpn. 2007, 80, 1162–1172; g) Y.
Imai, K. Murata, K. Kawaguchi, T. Sato, N. Tajima, R. Kuroda, Y.
Matsubara, Chem. Asian J. 2008, 3, 625–629; h) Y. Imai, K. Nagasa-
ki, K. Murata, K. Kawaguchi, T. Harada, Y. Nakano, T. Sato, M.
Fujiki, R. Kuroda, Y. Matsubara, CrystEngComm 2008, 10, 951–
953; i) Y. Imai, K. Kamon, K. Murata, T. Harada, Y. Nakano, T.
Sato, M. Fujiki, R. Kuroda, Y. Matsubara, Org. Biomol. Chem. 2008,
6, 3471–3475; j) Y. Ooyama, K. Yoshida, Eur. J. Org. Chem. 2008,
2564–2570; k) J. Luo, T. Lei, L. Wang, Y. Ma, Y. Cao, J. Wang, J.
Pei, J. Am. Chem. Soc. 2009, 131, 2076–2077; l) N. Shiota, T. Kinuta,
Figure 6. CPL and fluorescence spectra of complexes a) I, b) II, and c) III
in the solid state (as KBr pellets).
tions with I>2.0s(I); RACTHNUTRGNEUGN(all data)=0.0525; T=115(2) K. CCDC 822729
contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallograph-
ic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Chem. Asian J. 2012, 7, 360 – 366
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
365

Y. Imai et al.
FULL PAPERS
T. Sato, N. Tajima, R. Kuroda, Y. Matsubara, Y. Imai, Cryst. Growth
Des. 2010, 10, 1341–1345.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J.
Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C.
Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari,
J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cio-
slowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaro-
mi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng,
A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wall-
ingford CT, 2004.
[3] Lemmerer and co-workers have reported the crystal structure of
complex I. However, since the temperature of measurement was
173 K, we remeasured this complex at 115 K to unify the measure-
ment temperatures for complexes I–III. A. Lemmerer, S. A.
Bourne, M. A. Ferandes, CrystEngComm 2008, 10, 1605–1612.
[4] Determined by a PLATON geometry calculation.
[5] a) J. E. Ridley, M. C. Zerner, Theor. Chim. Acta 1973, 32, 111–134;
b) J. E. Ridley, M. C. Zerner, Theor. Chim. Acta 1976, 42, 223–236;
c) M. C. Zerner, G. H. Lowe, R. F. Kirchner, U. T. Mueller-Westerh-
off, J. Am. Chem. Soc. 1980, 102, 589–599.
[6] Gaussian 03, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schle-
gel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgom-
ery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S.
Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani,
N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
[7] R. Kuroda, Y. Saito, Bull. Chem. Soc. Jpn. 1976, 49, 433–436.
[8] SHELXL97, G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64,
112–122.
[9] A. L. Spek, PLATON,
A Multipurpose Crystallographic Tool,
Utrecht University, Utrecht (Netherlands), 2010.
[10] G. M. Sheldrick, SADABS, Program for Empirical Absorption Cor-
rection of Area Detector Data, University of Gçttingen, Gçttingen
(Germany), 1996.
Received: August 27, 2011
Published online: December 8, 2011
366
www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 360 – 366