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using a commercially available capacitance meter operating at 800 Hz
(Iso-Tech 9023). The capacitors were connected to the capacitance
High Efficiency and Quadratic
meter via Karl Süss MicroTec PH100 miniature probe heads. The Nonlinear Optical Properties of a Fully
measurement was repeated on a minimum of six spots located on the
whole length of anodized part of the foil. The leakage measurements Optimized 2D Octupolar Crystal
were performed directly after capacitance measurements using the
same connections. The bottom (Ti) electrode was biased either posi-
Characterized by Nonlinear
tively (as it was during anodization) or negatively (as it would be in a Microscopy**
p-type transistor). Subsequently, organic field-effect transistors were
fabricated by evaporating pentacene (97 %, Aldrich, used as received)
under a high vacuum < 5 10±7 torr with a rate of 0.3 nm s±1 at room By VØronique Le Floc'h, Sophie Brasselet,*
temperature. The pentacene film thickness measured with a Dektak Joseph Zyss, Bong Rae Cho,* Sang Hae Lee,
profilometer was ~ 50 nm. The transistors were completed by evapo- Seung-Joon Jeon, Minhaeng Cho, Kil Sik Min, and
ration of gold source and drain contacts through a shadow mask on
the top of the pentacene layer. The channel width and length was
Myunghyun Paik Suh
2 mm and 25 lm, respectively. Characterization was performed at am-
bient conditions without any special precautions. Two Keithley 2400 The study of octupolar molecules[1,2] has opened up new
source/measure units were used to control source±drain (VSD) and research directions in the design and synthesis of new families
gate (VG) voltages.
of molecules that have large nonlinear optical susceptibilities
Received: May 21, 2004 (hyperpolarizabilities), b, with possible applications in optical
Final version: July 12, 2004 and opto-electronic devices. Among the advantages of octu-
± polar structures is that they have a broader range of nonlinear
[1] A. I. Kingon, J. P. Maria, S. K. Streiffer, Nature 2000, 406, 1032. tensorial coefficients bijk (where i, j, k are the molecular-frame
[2] T. Inoue, T. Ohsuna, Y. Obara, Y. Yamamoto, M. Satoh, Y. Sakurai, indices) compared to earlier 1D schemes,[3] which provides an
Jpn. J. Appl. Phys., Part 1 1993, 32, 1765.
optimum nonlinear efficiency with a polarization-independent
[3] L. Manchanda, M. Gurvitch, IEEE Electron Device Lett. 1988, 9, 180.
[4] K. P. Pande, V. K. R. Nair, D. Gutierrez, J. Appl. Phys. 1983, 54, second-harmonic response to incident light. Optimization at
5436. the molecular level has made great progress, as exemplified
[5] P. K. Roy, I. C. Kizilyalli, Appl. Phys. Lett. 1998, 72, 2835. by the established structure±property relationship of two-di-
[6] H. Kim, D. C. Gilmer, S. A. Campbell, D. L. Polla, Appl. Phys. Lett. mensional octupoles and by the development of highly effi-
1996, 69, 3860.
cient molecules.[4±7] Different strategies have been proposed
[7] E. Becker, R. Parashkov, G. Ginev, D. Schneider, S. Hartmann,
F. Brunetti, T. Dobbertin, D. Metzdorf, T. Riedl, H.-H. Johannes,
to obtain a significant bulk second-order optical nonlinearity,
W. Kowalsky, Appl. Phys. Lett. 2003, 83, 4044. v(2), by the non-centrosymmetric alignment of octupoles such
[8] J. Tate, J. A. Rogers, C. D. W. Jones, B. Vyas, D. W. Murphy, W. Li, as optical poling in polymers,[8] supramolecular arrange-
Z. Bao, R. E. Slusher, A. Dodabalapur, H. E. Katz, Langmuir 2000, ment,[9±11] and crystal engineering.[12] Although the crystalline
16, 6054. structures would be more advantageous in terms of stability,
[9] Y. Iino, Y. Inoue, Y. Fujikake, H. Sato, M. Kawakita, S. Tokito,
achieving three-dimensional octupolar geometry at the mac-
H. Kikuchi, Jpn. J. Appl. Phys., Part 1 2003, 42, 299.
[10] L. A. Majewski, R. Schroeder, M. Grell, J. Phys. D: Appl. Phys.
2004, 37, 21.
[11] H. Y. Choi, S. H. Kim, J. Jang, Adv. Mater. 2004, 16, 732.
±
[12] A. W. Hassel, D. Diesing, Thin Solid Films 2002, 414, 296. [*] Dr. S. Brasselet, Dr. V. Le Floc'h, Prof. J. Zyss
Laboratoire de Photonique Quantique et MolØculaire (UMR 8537)
[13] Technical Notes of Aluminum Electrolytic Capacitors, Technical
Institut d'Alembert (IFR 121)
Note 8101C, Nichicon America, Schaumburg, IL. Ecole Normale SupØrieure de Cachan
[14] S. A. Campbell, H. S. Kim, D. C. Gilmer, B. He, T. Ma, W. L. Glad- 61 avenue du PrØsident Wilson
felter, IBM J. Res. Dev. 1999, 43, 383. F-94235 Cachan Cedex (France)
[15] R. B. van Dover, Appl. Phys. Lett. 1999, 74, 3041. E-mail: [Link]@[Link]
[16] J. Veres, S. D. Ogier, S. W. Leeming, D. C. Cupertino, Adv. Funct. Prof. B. R. Cho, Dr. S. H. Lee, Prof. S.-J. Jeon
Mater. 2003, 13, 199. Molecular Opto-Electronics Laboratory
[17] J. Veres, S. Ogier, S. Leeming, D. Cupertino, S. M. Khaffaf, G. Lloyd, Department of Chemistry and Center for Electro- and Photo-
Proc. SPIE-Int. Soc. Opt. Eng. 2003, 5217, 147. Responsive Molecules, Korea University
[18] T. W. Kelly, D. V. Muyres, P. F. Baude, T. P. Smith, T. D. Jones, Ma- 1-Anamdong, Seoul 136-701 (Korea)
ter. Res. Soc. Symp. Proc. 2003, 771, L6.5. E-mail: chobr@[Link]
[19] Y. Fujisaki, Y. Inoue, T. Kurita, S. Tokito, H. Fujikake, H. Kikuchi, Prof. M. Cho
Jpn. J. Appl. Phys., Part 1 2004, 43, 372. Department of Chemistry and Center for Multidimensional
Spectroscopy, Korea University
[20] J. Lee, K. Kim, J. H. Kim, S. Im, D. Y. Jung, Appl. Phys. Lett. 2003,
1-Anamdong, Seoul 136-701 (Korea)
82, 4169.
Dr. K. S. Min, Prof. M. P. Suh
[21] R. Schroeder, L. A. Majewski, M. Grell, Appl. Phys. Lett. 2003, 83,
Department of Chemistry, Seoul National University
3201.
Seoul 151-744 (Korea)
[22] S. M. Sze, Physics of Semiconductor Devices, 2nd ed., Wiley-VCH,
[**] This work is supported by a NRL grant, Creative Research Initiative
New York 1981, p. 447.
Program (KISTEP), and KOSEF. SHL was supported by the BK21
[23] J. P. Coling, J. W. Park, W. Xiong, IEEE Electron Device Lett. 2003, scholarship. We thank Prof. H. Ito (Tohoku University, Japan) for
24, 515. having provided the DAST crystal, and Prof. J.-F. Roch for helpful
[24] G. Wang, D. Moses, A. J. Heeger, H. M. Zhang, M. Narasimhan, discussions. Supporting Information is available online from Wiley
R. E. Demaray, J. Appl. Phys. 2004, 95, 316. InterScience of from the author.
196 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adma.200400451 Adv. Mater. 2005, 17, No. 2, January 31
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roscopic scale is non-trivial, and up to now, to the best of our peripheral phenyl rings. Tertiary amine nitrogen atoms exhibit
knowledge, octupolar crystals with large bulk nonlinearities sp2 hybridization instead of sp3 so that the whole molecule, ex-
have not been reported. Recently, we demonstrated that 1,3,5- cept for the terminal methyl groups, lies approximately in one
tricyano-2,4,6-tris(p-diethylaminostyryl)benzene (TTB) and plane. The important consequences of this planarity are i) an
its derivatives exhibit large first hyperpolarizabilities and sig- increased molecular hyperpolarizability value, b, due to effi-
nificant second-harmonic generation (SHG) in the powder cient charge transfer from the donor to the acceptor groups
state.[13] However, the origin of the bulk nonlinearity at the and ii) a potentially non-centrosymmetric arrangement of the
macroscopic level conjectured in the literature[1] has not been molecules in the crystal lattice, induced by the enhanced p±p
experimentally investigated. In this work, we show that the interlayer stacking interactions.
TTB crystal has a non-centrosymmetric octupolar structure, The three-dimensional arrangement of TTB in the crystal
which facilitates optimal transfer of the molecular hyperpolar- unit cell is shown in Figure 1b. It consists of three molecules
izability components to the macroscopic level. Indeed, in other packed along the c-axis with a slight offset. The p±p stacking
types of structures such as dipolar or multipolar crystals, the interactions between adjacent molecules stacked in neighbor-
macroscopic symmetry is often different from the molecular ing layers play a crucial role in the formation of the non-cen-
one, which results in a decrease in efficiency upon projecting trosymmetric crystal.[14] Intermolecular herringbone p±p in-
the molecular tensorial components onto the macroscopic teractions between the phenyl groups in the side chains of
frame. The TTB crystal, which does not suffer from such draw- neighboring molecules within the same layer can also contrib-
backs, consequently exhibits a very large bulk nonlinearity. ute to the final three-dimensional non-centrosymmetric ar-
The TTB single crystals were obtained by slowly evaporat- rangement. This confirms that a planar octupolar molecule
ing a saturated solution of TTB in CH2Cl2±EtOEt. The crys- with long ªarmsº containing aromatic rings that can induce
tals were cylindrical in shape with hexagonal cross-sections, non-negligible p±p interactions (and thus minimize any void
and their sizes ranged from several micrometers to several volume in a given unit cell) is most likely to form a non-cen-
millimeters. The X-ray structure of the octupolar molecule is trosymmetric crystal, based on the Kitaigorodskii closest-
shown in Figure 1a; four benzene moieties lie in the same packing paradigm for molecular crystal structures.[15]
plane, with dihedral angles of ca. 30 between the central and To confirm optically the octupolar crystalline structure and
determine the molecular arrangement inside the submilli-
meter-sized crystal, we applied a polarized nonlinear micros-
(a) copy analysis technique combining second harmonic genera-
tion (SHG) and two-photon fluorescence (TPF). This unique
methodology is based on the interplay of two complementary
optical effects that have recently been shown to allow the res-
olution of complex molecular arrangements.[16] The TTB crys-
tal, lying on a microscope slide, was illuminated in the non-
linear microscopy setup either sideways along its cylindrical
axis or from the top along its hexagonal face. The IR exciting
beam originating from a femtosecond titanium/sapphire
(Ti:Sa) laser (150 fs, 86 MHz repetition rate) was focused
onto the crystal using a high-numerical-aperture (high-NA)
objective (NA: 1.4; 60) with a spatial resolution of about
400 nm and a typical pulse energy of the order of 3 pJ, at a
(b) (c) Z fundamental wavelength of 1028 nm. The emitted TPF and
z=3 SHG signals were collected by the same objective. A beam
θ splitter directed the emitted signals to a spectrograph and the
c resulting spectrum exhibited the SHG peak at half the inci-
1=a 1 dent wavelength (514 nm), well-separated from the fluores-
Ψ Y
b cence emission band, which was around 710 nm (see Support-
x ing Information). The SHG or TPF signals were therefore
φ y
easily detectable using appropriate spectral filters. The signals
X were then directed to a polarization analysis set-up operating
Figure 1. a) TTB structure drawn using the software ORTEP. b) Unit-cell
in the photon-counting regime, the perpendicularly polarized
structure of the TTB crystal. The 1-axis is chose to be parallel to one of signals being simultaneously recorded on two avalanche
the C2-axes. c) Definition of the Euler angles (h,u,w) in the macroscopic photodiodes. Two perpendicular polarization states were thus
framework (X,Y,Z), given the orientation of the unit-cell framework detected, while the incident polarization was rotated in the
(1,2,3): the (h, u) angles define the orientation of the x-y molecular plane
plane of the microscope slide (X-Y plane) using a rotating
in the macroscopic (X,Y,Z) frame. The TTB molecules, represented by the
plain lines, lie in the x-y plane, with an orientation angle w between the half-wave plate (Fig. 1c). The incident polarization direction,
x- and 1-axes. E, is defined by the angle U = (X,E), (i.e., the angle between
Adv. Mater. 2005, 17, No. 2, January 31 [Link] 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 197
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X and E) which was varied from 0 to 360 . Polarization cali-
brations suggested that ellipticity and dichroism parameters
had to be duly taken into account, because of the reflection of
the incident beam on the dichroic mirror.[16]
The TPF and SHG polarization responses can be expressed
as a function of the unit-cell orientation (h,u,w) within the
crystal as described in Figure 1c. The corresponding intensi-
ties, S, analyzed along a given direction, I, are given by[16]
P
STPF
I = aII c E E E E (U)
JKLM JKLM J K L M
(1)
and
P
SSHG
I = b b E E E E (U)
JK IJK ILM J K L M
(2)
where the indices I, J, K, L, and M refer to coordinates in the
macroscopic framework and Ex (x = J, K, L, M) is the x-com-
ponent of the incident field. The notation (_) denotes the
temporal average over the detector integration time of (_),
while a represents the one-photon emission tensor, c the two- Figure 2. Polar diagrams representing the SHG (a,c) and the TPF (b,d)
intensities as functions of the incident polarization angle U. Experimen-
photon excitation tensor, and b the hyperpolarizability tensor.
tal data SX (in dark gray) and SY (in light gray) in counts/100 ms were ob-
These tensors can be expressed in the macroscopic framework tained using an incident-beam power of 200 lW. The continuous lines
using the purely additive oriented gas model.[17] In such a correspond to the intensity fits with the following orientation parameters:
scheme, aIJ(h,u,w) = åijaij cos (i,I) cos (j,J) (and similar ex- a,c) (90 ,30 ,±5 ) and b,d) (90 ,30 ,88 ). An ellipticity parameter of
e = 1.57 rad and an amplitude dichroism factor d = ±0.02 at 1028 nm [16]
pressions for the c and b tensors), with cos (i,I) being the pro-
accounted for the incident-field ellipticity. The crystal directions are repre-
jections of the i = (1,2,3) axes on the I = (X,Y,Z) axes, which sented by the dark rectangles.
are dependent on (h,u,w). The application of such a model,
which a priori ignores intermolecular interactions, is justified
by the experimental results. Assuming an octupolar planar lying on its hexagonal face exhibited four-lobed patterns
symmetry of the molecular arrangement within the TTB crys- (Fig. 3). These patterns remained invariant for any p/3 rota-
tal, the unit-cell tensor coefficients
p aij, bijk, and cijkl, are only tion of the crystal in its plane. Such a result provides clear evi-
limited to a11 = a22 = 1/ 2iai (with iai = åija2ij), c1111 = c2222 dence of the threefold symmetry in the plane of the hexagonal
= 0.612ici, c1122 = c2211 = c1221 = c2112 = c2121 = c1212 = c1111/3 face, which stands out as a clear characteristic feature of octu-
= 0.204ici, and b111 = ±b122 = ±b212 = ±b221 = 0.5ibi. By fitting
the (h,u,w) values to the experimental data with the variable
U, it is possible to confirm the octupolar structure of the crys-
talline unit cell as well as to determine the orientation of the
octupoles within the crystal lattice.
The TPF and SHG signals were first analyzed in a config-
uration where the crystal lay along one of its sides with differ- 16°
ent orientations in the X±Y plane, as displayed in Figure 2. In
this configuration, the best agreement with the data was ob-
tained when h = 90 , which corresponds to the case where the
octupole planes lie edgeways, i.e., perpendicular to the X±Y
plane. The orientation of the crystal side in the sample plane
was then fully defined solely by the angle u , while the
in-plane w angle became irrelevant. The crystal orientation
angles retrieved from the fits corresponded to the expected
orientations in the (X,Y,Z) framework. The polarization
features were characteristic of a planar-molecular stacking
direction in the crystal. Indeed, the two-lobed pattern was
perpendicular to the cylindrical axis and followed the rotation
of the crystal, which is a signature of the anisotropism of the Figure 3. Polar diagrams representing the SHG (a,b) and the TPF (c,d)
projection of octupoles lying perpendicular to the sample intensities as functions of the U angle with the crystal lying on its hexag-
onal face. Experimental data SX (in dark gray) and SY (in light gray) in
plane and parallel to the hexagonal face. counts/100 ms were obtained using an incident beam power of 56 lW.
In contrast to the previously depicted ªsidewaysº configura- The continuous lines correspond to the intensity fits with the Euler an-
tions, the TPF and SHG polarization responses of the crystal gles (0 ,0 ,16 ).
198 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] Adv. Mater. 2005, 17, No. 2, January 31
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polar molecular structures. Note that the sum of the optical in tetrahydrofuran (THF) (which is well adapted to octupolar
signals for the two X and Y analysis directions gives, for both molecules[11,12,23,24]) and led to b111,TTB = 407 10±30 esu at zero
SHG and TPF, four-lobed patterns oriented along the X- and frequency.[24] Assuming that the crystal refractive indices at
Y-directions, instead of the circular pattern expected from the wavelength, x, are nx1 = nx2 = 1.5, and accounting for the crystal
polarization-independent SHG response for octupolar sym- molecular density in the oriented gas model, we obtain
metry.[18] This deviation is due to the ellipticity of the incident idiTTB = 2297 10±9 esu at zero frequency, which is approxi-
laser beam introduced by the dichroic mirror, which affected mately three times larger than that of the DAST crystal. Such a
intermediate polarizations. The fits of the experimental data factor is of the same order of magnitude as the one measured
were obtained with h = 0 , as expected, u = 0 , and w = 16 using nonlinear microscopy, with a discrepancy due to the error
(which represents the orientation of the hexagon in the X±Y bars in the previous estimation and to the fact that the hyper-
plane). Note that the polarization responses obtained in Fig- Rayleigh measurements were performed in solution where lo-
ure 3 are the specific signature of threefold planar symmetry, cal field factors may have been different. The efficiency differ-
and would be unattainable with a different multipolar symme- ence between DAST and TTB is mainly due to both the lower
try. molecular efficiency of the dipolar DAST molecule (the high-
The slight discrepancy between the model and the experi- est published value is b111,DAST = 110 10±30 esu at zero fre-
ment regarding the shape and orientation of the four-lobed quency[25]) and the less-favorable projection factors induced by
structure can be due either to the integration of the signals the DAST unit-cell symmetry (which belongs to polar space
over the Rayleigh length of the objective focus (about 2 lm), group Cc[20]).
or to interface effects between the crystal surface and the mi- In conclusion, a rational design strategy, which takes advan-
croscope slide. Deviations from Kleinman symmetry relations, tage of favorable interlayer p±p interactions in stacked mole-
due to the resonant conditions of the experiment, only slightly cules, is proposed for the synthesis of an octupolar crystal with
affected the four-lobed shapes and have thus been omitted a large SHG efficiency. Optical polarization measurements of
from the model. In addition to confirming the molecular-or- both SHG and TPF confirmed the non-centrosymmetric
der symmetry, the nonlinear optical responses of the crystal threefold symmetry of the TTB crystal, which allowed opti-
were also found to be perfectly uniform on scanning over the mum use of the molecular hyperpolarizability components, re-
whole crystal surface area of the sample. The results of Fig- sulting in a very large bulk nonlinearity.
ures 2,3 show, furthermore, that the oriented gas model, al-
though not accounting for the strong p±p interactions be-
tween adjacent molecules, applies to the nonlinear response Experimental
of the structure studied. This is mostly due to the nature of
such interactions, which are locally centrosymmetric (al- Optical Calibration Procedure: Previous studies [16] have shown
though they contribute to the overall non-centrosymmetry) that in the (X,Y,Z) framework, the exciting beam at the point of focus
can be written as
and provide a negligible contribution to the induced polariza- r
tions at the incident wavelength, 1028 nm. E U; e; d; xt E 1 1 d2
In order to evaluate the SHG efficiency, idi, of the octupo-
lar crystal, we compared the SHG signal intensity of TTB to cosU cosxt; 1 d sinU cos xt e; 0 (3)
that of a reference 4-dimethylamino-N-methyl-4-stilbazolium
tosylate (DAST)[19,20] crystal, which has very similar absorp- where E is the field amplitude. The parameters d and e account re-
spectively for the dichroism and ellipticity of the field polarization
tion characteristics (both crystals exhibit a cut-off wavelength upon reflection by the dichroic mirror. They are measured separately
at about 600 nm, with a large absorption centered at about by standard ellipsometry (e = 1.57 rad and d = ±0.02 at 1028 nm). The
500 nm). The experimental data, corrected for the incident polarization direction, U, was varied from 0 to 360 by using a rotat-
power, resulted in idiTTB » 2 idiDAST at the 1028 nm incident ing half-wave plate inserted in the linear-excitation polarization
control set-up. The DAST crystal, used as a reference, exhibited a
wavelength. The DAST crystal is well-known for its very large quasi-identical absorption spectrum. The calibration of the nonlinear
efficiency (idiDAST = 790 10±9 esu at 1.55 lm from published microscope efficiency was carried out using polarization measure-
data[21]); the TTB crystal is therefore among the most efficient ments on a DAST crystal lying on its [001] face, which gave very spe-
organic crystals with idiTTB » 1580 10±9 esu under non-reso- cific polar patterns, for which the fits were in good agreement with
the expected symmetry. This crystal could therefore have been consid-
nant conditions. The precision of this measurement was be-
ered for use as a reference in measurements of unknown idi values.
tween 20 % and 30 % because of the sensitivity of the SHG The proportionality coefficient introduced to fit the SHG signals was
signal to focalization and crystal positioning on the micro- indeed proportional to idi2Pinc
2
, where Pinc represents the peak power
scope slide. Note that the idi coefficients contain the molecu- of the IR radiation incident on the crystal.
lar densities (NTTB = 9.92 1020 molecules cm±3 and Received: March 25, 2004
NDAST = 1.91 10 molecules cm±3 from the X-ray structure
21
Final version: July 23, 2004
of the crystals), the local field factors, and the molecular
b-efficiencies.
±
[1] J. Zyss, Nonlinear Opt. 1991, 1, 3.
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[4] V. R. Thalladi, S. Brasselet, D. Bläser, R. Boese, J. Zyss, A. Nangia,
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[5] C. Andraud, T. Zabulon, A. Collet, J. Zyss, Chem. Phys. 1999, 245, Molded from Morphology-Tunable and
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[6] Y.-K. Lee, S.-J. Jeon, M. Cho, J. Am. Chem. Soc. 1998, 120, 10 921. Recyclable Organic Templates of
[7] J. Brunel, I. Ledoux, J. Zyss, M. Blanchard-Desce, Chem. Commun. Hydrogen-Bonded Supramolecular
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[8] C. Fiorini, F. Charra, J.-M. Nunzi, I. D. W. Samuel, J. Zyss, Opt. Lett. Assemblages**
1995, 20, 2469.
[9] S.-H. Kang, Y. S. Kang, W.-C. Zin, G. Olbrechts, K. Wostyn, K. Calys, By Masaru Nakagawa,* Daisuke Ishii, Ken'ichi Aoki,
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[11] H. Le Bozec, T. Le Bouder, O. Maury, A. Bondon, I. Ledoux, S. De- Since the discovery of sheet-curled chrysotile,[1] polypyr-
veau, J. Zyss, Adv. Mater. 2001, 13, 1677. role,[2] and carbon nanotubes,[3] organic and inorganic tubular
[12] V. R. Thalladi, S. Brasselet, H.-C. Weiss, D. Bläser, A. K. Katz, H. L. materials have attracted much attention due to their unique
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[13] B. R. Cho, S. B. Park, S. J. Lee, K. H. Son, S. H. Lee, M.-J. Lee,
sis is widely accepted as a simple, high-throughput, and cost-
J. Yoo, Y. K. Lee, G. J. Lee, T. I. Kang, M. Cho, S.-J. Jeon, J. Am. effective method for the fabrication of tubular fibers com-
Chem. Soc. 2001, 123, 6421. posed of metal sulfides and oxides,[5] metals,[6] or conducting
[14] Intermolecular distances relative to p±p interactions. Offset face to polymers[7] through sol±gel polymerization,[8] electroless[9] or
face p±p interactions: 1) For the benzene ring composed of carbon electrochemical[10] plating, or vapor deposition.[11] The inner
atoms C1 to C6 (bz(C1±C6)) and bz(C12±C17(±y + 1, x ± y, z + 1/3)):
surfaces of porous anodic alumina[12] and the outer surfaces of
centroid separation = 4.832 ; dihedral angle = 25.7 . 2) For bz(C1±
C6) and bz(C1±C6(±y + 1, x ± y, z + 1/3, or ±x + y + 1, ±x + 1, z ± 1/3)): lipid-based cylindrical tubules,[13] organic gelator fibrils,[14] sin-
centroid separation = 5.115 ; dihedral angle = 7.97 . 3) For bz(C12± gle- and double-headed amphiphile molecular assemblages,[15]
C17) and bz(C36±C41(±x + y + 1, ±x + 1, z ± 1/3)): centroid separa- carbon nanotubes,[16] and electrospun degradable polymer fi-
tion = 5.464 ; dihedral angle = 4.96 . Edge-to-face p±p interactions: bers[17] have been utilized as reliable templates for the fabrica-
1) For bz (C12±C17) and bz(C24±C29(±y + 1, x ± y, z + 1/3)): centroid
tion of tubular fibers. Many efforts are currently being made
separation = 5.483 ; dihedral angle = 63.1 . 2) For bz(C24±C29) and
bz(C36±C41(±y + 1, x ± y, z + 1/3)): centroid separation = 5.303 ; di-
to control the inner diameter and even the entire morphology
hedral angle = 68.0 . of these tiny tubular materials.
[15] A. I. Kitaigorodskii, Molecular Crystals and Molecules, Academic We have reported previously that the amphoteric com-
Press, New York 1973. pound 6-[2-propyl-4-(4-pyridylazo)phenoxy]hexanoic acid (1,
[16] V. Le Floc'h, S. Brasselet, J.-F. Roch, J. Zyss, J. Phys. Chem. B 2003, Fig. 1) self-organizes upon neutralization of its alkaline aque-
107, 12 403.
ous solution to give fibrous molecular assemblages.[18a] Atom-
[17] J. Zyss, J.-L. Oudar, Phys. Rev. A 1982, 26, 2028.
[18] J. Zyss, S. Brasselet, V. R. Thalladi, G. R. Desiraju, J. Chem. Phys.
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______________________ Prof. T. Iyoda
CREST-JST
JST, 4-1-8 Honmachi, Kawaguchi, Saitama 332-0012 (Japan)
[**] This study was carried out at the Chemical Resources Laboratory of
the Tokyo Institute of Technology. We thank Yukari Dan of Hitachi
Science System, Ltd. and Hidehiro Yamada of Hitachi High-Technol-
ogies Corporation for their assistance with the SEM observations.
We also thank Taichi Nagashima and Mitsuhide Yamada of Osaka
Gas Ltd. for their help with the XPS measurements.
200 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adma.200400520 Adv. Mater. 2005, 17, No. 2, January 31