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Herein, we describe the synthesis of a low-symmetry mono- zene rings form crystalline and amorphous domains. Upon
dendron, 3,4-bis(dodecyloxy)-5-[3,4,5-tris(dodecyloxy)benzyl- cooling from the isotropic melt the compound exhibits a
oxy]benzoic acid, following a simple route which starts from monotropic smectic mesophase. In 100-nm-thick films on a
gallic acid ethyl ester and does not require any protecting neutral substrate the structure loses its biaxiality, adopting a
groups. The self-assembled structures formed by the com- hexagonal columnar structure with the columns oriented paral-
pound in 3D and 2D were investigated by synchrotron X-ray lel to the substrate. By contrast, in ultrathin films on graphite
scattering and scanning force microscopy (SFM). In 3D, the the SFM likely reveals two crystal orientations, which can de-
compound forms a stable crystalline phase with an orthorhom- velop due to the epitaxial adsorption on the substrate of the
bic lattice in which the alkyl chains connected to different ben- alkyl chains pertinent to different benzene rings.
1. Introduction
3638 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2010, 11, 3638 – 3644
Self-Assembly of Low-Symmetry Monodendron
ChemPhysChem 2010, 11, 3638 – 3644 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 3639
H. Keul, D. A. Ivanov et al.
smectic or columnar liquid-crystalline phase (cf. for example thermal expansion becomes positive with the value typical of
ref. [9]). It is likely that the compound crystallizes upon further organic crystals aCr = 1.1 10 4 K 1.[21] In this temperature range
cooling to 14 8C, since the enthalpy of this transition is rather an additional crystalline peak, which corresponds to crystalliza-
high. The DSC curve obtained during the second heating ap- tion of the alkyl chains, appears in the diffractograms at
pears to be rather complex: it reveals a number of endother- s = 0.24 1.
mic and exothermic peaks. This signifies that compound A un- A typical X-ray diffractogram of a fiber of A recorded at
dergoes several phase transitions before isotropization. To room temperature is shown in Figure 5. In contrast to the
identify the different phases formed by compound A we car- sample that was freshly cooled to 0 8C (Figure 3), the sample
ried out synchrotron XRD experiments at variable tempera-
tures.
The XRD measurements were performed on fibers of com-
pound A extruded from the mesophase. By cooling the sam-
ples from the isotropic melt, a smectic liquid-crystalline phase
was formed at 48 8C (Figure 3). This is slightly higher than the
3640 www.chemphyschem.org 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2010, 11, 3638 – 3644
Self-Assembly of Low-Symmetry Monodendron
ChemPhysChem 2010, 11, 3638 – 3644 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 3641
H. Keul, D. A. Ivanov et al.
than the two other peaks of the lattice, the direction of the 3. Conclusions
columns is isotropic in the plane of the substrate. The lattice
of compound A in thin films substantially differs from the one A new low-symmetry monodendritic molecule functionalized
in the bulk. It is thus likely that the conditions of sample prep- with a carboxylic group at the focal point, 3,4-bis(dodecyloxy)-
aration and geometrical confinement limit molecular mobility, 5-[3,4,5-tris(dodecyloxy)benzyloxy]benzoic acid, was synthe-
thereby impeding the formation of a regular three-dimensional sized in high yield via a simple route starting from gallic acid
lattice. In this case, the structure of A in the direction perpen- ethyl ester without the need for protecting groups. The result-
dicular to the columnar axis loses its asymmetry and exhibits ing compound was characterized by a combination of DSC,
only one characteristic distance close to the a-parameter of POM, and XRD. It was shown that the compound exhibits a
the 3D crystalline phase described above (Table 1). stable rectangular columnar crystalline phase and a monotrop-
Figure 10 shows the morphology of an ultrathin film of A on ic smectic phase formed upon cooling from the isotropic melt.
graphite after annealing the sample at 45 8C. The SFM height In the crystalline structure the columns with noncircular cross
image, generated in tapping mode, reveals two morphological section are formed due to specific arrangement of crystalline
and amorphous domains of alkyl chains.
The structure of the compound crucially depends on the
conditions of the geometrical confinement. Thus, a 100-nm-
thick film reveals a columnar hexagonal phase with the col-
umns oriented parallel to the substrate.
The SFM investigation of ultrathin films of the compound on
graphite likely shows two crystal orientations that can develop
due to epitaxial adsorption of the alkyl chains attached to dif-
ferent benzene rings.
This compound exhibits a very peculiar structure in which
three alkyl chains crystallize and the other two remain in the
amorphous state. Meanwhile the crystalline and amorphous
domains are well-ordered in 3D. Such a structure might be
used to create membranes for gas separation. Furthermore,
the compound is a unique building block for the construction
of new functional materials. Different groups such as crown
ether and sulfonic acid can be linked to the acid site. This
Figure 10. Height and phase images of a thin film of A on HOPG acquired in could lead to the formation of various fascinating structures.
tapping mode. The arrows (left image) point at smooth adlayers with a mo-
lecular thickness of 4.2 (cf. cross section). This featureless film coexists
with a substructured layer (right image). The inset is a phase image to high-
light the substructure. The power spectral density (PSD) indicating an in- Experimental Section
plane periodicity of 43 is shown at the bottom.
Materials
1-Bromododecane (97 %), LiAlH4 (95 + %), SOCl2 (99 + %), NaOH
traits. The first is a featureless layer with a thickness of 4.2 , (97 %), ethyl 3,4,5-trihydroxybenzoate (98 %), and anhydrous K2CO3
which is close to the c-parameter of the crystalline lattice mea- (all from Aldrich) were used as received. DMF was dried over calci-
sured by XRD. The sharp edges of this layer indicate on its um hydride (CaH2) for 12 h and distilled under vacuum.
crystalline nature (right image in Figure 10). The second is a
substructured layer with less defined height. The inner sub-
structure is better resolved in the phase image where the Synthesis
stripes with a periodicity of 43 can be seen (insert,
Ethyl 3,4-bis(dodecyloxy)-5-hydroxybenzoate (2 a) and Ethyl 3,4,5-
Figure 10). This periodicity is close to the a-parameter of the
tri(dodecyloxy)benzoate (2 b): Anhydrous K2CO3 (4.44 g, 32 mmol,
crystalline lattice. 2 eq) and 1-bromodecane (8 g, 32 mmol, 2 eq) were added to a so-
The two morphologies may simply correspond to two differ- lution of gallic acid ethyl ester (3.18 g, 16 mmol, 1 eq) in dry DMF
ent crystal orientations of A on graphite. The thickness of the (60 mL). The mixture was heated at 120 8C under N2 atmosphere
smooth layer matches the c-parameter of the unit cell, thus for 20 h. The reaction mixture was allowed to cool to room tem-
the crystal is oriented with its ab-plane lying on the substrate. perature before water (150 mL) was added. The formed brownish
The elongated stripes would then correspond to a crystal ori- precipitate was filtrated and dried in vacuo. A brownish solid was
entation in which the ac-plane runs parallel to the substrate. In obtained, a mixture of 2 a, 2 b, and 2 c, which were successfully
separated using column chromatography (silica gel, hexane/ethyl
the first orientation, the alkyl chains can probably extend
acetate = 9/1).
easier on the graphite surface toward which they have a spe- 2 a: 1H NMR (300 MHz, CDCl3, TMS): d = 0.88 (t, 3 H), 1.26 (m, 36 H),
cial affinity (Figure 8). However, even for the second orienta- 1.37 (t, overlapped, 3 H), 1.75 (m, 4 H), 4.03 (t, 2 H), 4.15 (t, 2 H), 4.33
tion the epitaxial interactions of the alkyl chains with the (q, 2 H), 5.88 (s, 1 H), 7.18 (d, 1 H), 7.29 ppm (d, 1 H); 13C NMR
graphite surface are not excluded. (75 MHz, CDCl3, TMS): d = 14.1, 14.3, 22.7, 25.9, 26.2, 29.3, 29.4,
3642 www.chemphyschem.org 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2010, 11, 3638 – 3644
Self-Assembly of Low-Symmetry Monodendron
29.4, 29.6, 29.7, 30.2, 31.9, 61.0, 68.9, 73.6, 76.7, 77.0, 77.4, 106.4, Polarizing Optical Microscopy: POM analyses were performed with
125.6, 138.6, 149.1, 151.3, 166.3 ppm. a Zeiss AXIOPLAN 2 polarizing microscope, equipped with a
2 b: 1H NMR (300 MHz, CDCl3, TMS): d = 0.88 (t, 3 H), 1.27 (m, 54 H), METTLER FP 90 hot stage. Images were taken with a digital Zeiss
1.38 (t, overlapped, 3 H), 4.02 (t, 6 H), 4.34 (q, 2 H), 7.26 ppm (s, 2 H); AxioCam MRC4 camera in combination with Zeiss AxioVision soft-
13
C NMR (75 MHz, CDCl3, TMS): d = 14.1, 14.4, 22.7, 26.1, 29.4, 29.4, ware.
29.6, 29.7, 29.7, 30.4, 32.0, 61.0, 69.2, 73.5, 108.0, 125.1, 142.3,
Differential Scanning Calorimetry: DSC measurements were per-
152.8, 166.5 ppm.
formed using a Netzsch DSC 204 unit. Samples (typical weight:
[3,4,5-Tris(dodecyloxy)phenyl]methanol (3 b): Ester 2 b (2 g, 5 mg) were enclosed in standard Netzsch aluminium crucibles.
2.85 mmol, 1 eq) was dissolved in THF (20 mL) and cooled down to Indium and palmitic acid standards were used for calibration. The
0 8C. Then LiAlH4 (130 mg, 3.42 mmol, 1.2 eq) was added in small heating and cooling rates were 10 8C min 1.
portions and the reaction mixture was stirred at room temperature
Scanning Force Microscopy: SFM investigations were carried out
overnight. Then the reaction mixture was cooled to 0 8C and water
with a multimode AFM (NanoScope IIIa, Digital Instruments Veeco
(2 mL) was added slowly. The reaction mixture was diluted with
Instruments, Santa Barbara, CA) under ambient conditions. Com-
THF, the ice bath was removed and an aqueous solution (5 mL) of
mercially available silicon cantilevers (PPP-SEIH-W from Nanosen-
NaOH (456 mg, 11.4 mmol, 4 eq) water added. The inorganic pre-
sors) with a nominal spring constant of 5–40 N m 1 and a reso-
cipitate formed was filtered and disposed. The solvent was evapo-
nance frequency of 70–300 kHz were used. The tapping-mode to-
rated and the product recrystallized from acetone yielding 1.54 g
pography and phase images were processed with the Digital In-
white powder. Yield: 77 %. 1H NMR (300 MHz, CDCl3, TMS): d = 0.88
struments NanoScope software (version 5.12r5).
(t, 3 H), 1.27 (m, 54 H), 1.76 (m, 6 H), 3.96 (m, 6 H), 4.57 (s, 2 H),
6.54 ppm (s, 2 H); 13C NMR (75 MHz, CDCl3, TMS): d = 14.1, 22.7, X-Ray Diffraction: XRD experiments were carried out on the BM26B
25.8, 26.1, 29.4, 29.7, 29.7, 29.8, 30.3, 32.0, 65.5, 69.0, 73.5, 105.3, beamline[24] at the European Synchrotron Radiation Facility (ESRF,
136.2, 153.2 ppm. Grenoble, France) with a Frelon CCD camera. A wavelength of
1.24 was used. Oriented fibers with a diameter of 0.5 mm were
5-(Chloromethyl)-1,2,3-tris(dodecyloxy)benzene (4 b): [3,4,5-Tris(do-
extruded at room temperature after rapid cooling from melt using
decyloxy)phenyl]methanol (1 g, 1.51 mmol, 1 eq) was dissolved in
a homemade mini-extruder. Variable-temperature measurements
chloroform (20 mL) and cooled to 0 8C. Thionyl chloride (198 mg,
were carried out in a Linkam heating stage using an acquisition
1.66 mmol, 1.1 eq) in chloroform (2 mL) was added dropwise and
time of 24 s. Small-angle X-ray scattering measurements were per-
the reaction mixture was stirred under N2 atmosphere at room
formed with a 2D gas detector at a sample–detector distance of
temperature for 1 h. The solvent and excess of thionyl chloride
1.5 m. The modulus of the scattering vector s (s = 2 sinV/l, where
were evaporated in vacuo and the slightly yellowish solid obtained
V is the Bragg angle and l the wavelength) was calibrated using
was used immediately for the next step. Yield: 100 %.
several diffraction orders of silver behenate.
Ethyl 3,4-bis(dodecyloxy)-5-[3,4,5-tris(dodecyloxy)benzyloxy]ben-
Grazing Incidence Wide-Angle X-Ray Scattering: GIWAXS experi-
zoate (5): Freshly prepared chloride 4 b (1.04 g, 1.51 mmol, 1 eq)
ments were conducted on the ID10 beamline of the ESRF using a
was placed in DMF (30 mL) and anhydrous K2CO3 (0.42 g,
wavelength of 1.55 and an incidence angle of 0.28. The samples
3.02 mmol, 2 eq) and 2 b (0.82 g, 1.51 mmol, 1 eq) were added. The
for GIWAXS were prepared by spin-coating of a 10 mg mL 1 solu-
mixture was heated under N2 atmosphere at 120 8C for 24 h and
tion of A in chloroform on cleaned silicon wafers. The scattering
poured hot into ice water (250 mL). The product was filtered and
was recorded with a MAR CCD camera.
dried, yielding a yellowish solid (1.7 g). Yield: 96 %. 1H NMR
(300 MHz, CDCl3, TMS): d = 0.88 (t, 3 H), 1.26 (m, 90 H), 1.39 (t, over-
lapped 3 H) 1.79 (m, 10 H), 3.96 (m, 10 H), 4.34 (q, 2 H), 5.02 (s, 2 H), Acknowledgements
7.29 ppm (s, 1 H); 13C NMR (75 MHz, CDCl3, TMS): d = 14.1, 14.4,
22.7, 26.1, 26.2, 29.3, 29.4, 29.5, 29.6, 29.7, 29.7, 30.4, 32.0, 61.0,
69.1, 71.5, 73.4, 73.6, 76.7, 77.0, 77.2, 77.4, 105.7, 108.3, 109.1,
The authors acknowledge the French Agence Nationale de la Re-
125.1, 132.0, 137.7, 142.6, 152.3, 152.9, 153.2, 166.3 ppm. cherche (projects SPIRWIND and T2T) and Deutsche Forschungs-
gemeinschaft (Project T2T) for financial support. The authors ac-
3,4-Bis(dodecyloxy)-5-[3,4,5-tris(dodecyloxy)benzyloxy]benzoic acid
knowledge the European Synchrotron Radiation Facility for pro-
(A): Ester 5 (0.9 g 0.764 mmol, 1 eq), KOH (0.172 g, 3.06 mmol,
viding the excellent environment for X-ray measurements. We are
4 eq), ethanol (30 mL), and water (5 mL) were refluxed for 12 h.
Then the reaction mixture was cooled to 30–40 8C and concentrat- grateful to W. Bras and G. Portale (BM26, ESRF) and to O. Kono-
ed hydrochloric acid was added carefully until a pH of 1 was valov (ID10, ESRF) for assistance in the diffraction experiments
reached. The white precipitate formed was filtered and dried in and fruitful discussions.
vacuo. Yield: 85 %. 1H NMR (300 MHz, CDCl3, TMS): d = 0.88 (t, 3 H),
1.26 (m, 90 H), 1.82 (m, 10 H), 3.97 (m, 10 H), 5.04 (s, 2 H), 6.66 (s,
2 H), 7.36 (d, 1 H), 7.41 ppm (d, 1 H); 13C NMR (75 MHz, CDCl3, TMS):
Keywords: monodendrons · phase transitions · self-assembly ·
d = 14.1, 22.7, 26.1, 26.2, 29.3, 29.4, 29.4, 29.5, 29.6, 29.7, 30.4, 32.0, thin films · X-ray diffraction
69.1, 71.5, 73.4, 73.7, 105.9, 108.9, 109.7, 123.8, 131.8, 137.8, 143.5,
152.4, 153.0, 153.2, 171.6 ppm. [1] S. Chandrasekhar, B. K. Sadashiva, K. A. Suresh, Pramana 1977, 9, 471 –
480.
[2] R. I. Gearba, A. Bondar; M. Lehmann, B. Goderis, W. Bras, M. H. J. Koch,
D. A. Ivanov, Adv. Mater. 2005, 17, 671 – 676, B. Goderis, W. Bras, D. A.
Characterization Ivanov, Chem. Mater. 2005, 17, 2825 – 2832.
[3] M. Lehmann, R. I. Gearba, M. H. J. Koch, D. A. Ivanov, Chem. Mater. 2004,
NMR Spectroscopy: 1H NMR (300 MHz) and 13C NMR (75 MHZ) spec- 16, 374 – 376.
tra were recorded on a Bruker DPX-300 spectrometer in chloroform [4] V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc.,
(CDCl3) with tetramethylsilane (TMS) as internal standart at 20 8C. Perkin Trans. 1 1993, 1411 – 1420.
ChemPhysChem 2010, 11, 3638 – 3644 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 3643
H. Keul, D. A. Ivanov et al.
[5] U. Beginn, Prog. Polym. Sci. 2003, 28, 1049 – 1105. [16] F. C. Yu, L. J. Yu, Chem. Mater. 2006, 18, 5410 – 5420.
[6] S. Kumar, Chem. Soc. Rev. 2006, 35, 83 – 109. [17] X. Zhu, M. A. Scherbina, A. V. Barikov, B. Gorzolnik, S. N. Chvalun, U.
[7] V. Percec, A. E. Dulcey, M. Peterca, M. Ilies, J. Ladislaw, B. M. Rosen, U. Beginn, M. Mçller, Chem. Mater. 2006, 18, 4667 – 4673.
Edlund, P. A. Heiney, Angew. Chem. 2005, 117, 6674 – 6679; Angew. [18] K. Kishikawa, S. Nakahara, Y. Nishikawa, S. Kohmoto, M. Yamamoto, J.
Chem. Int. Ed. 2005, 44, 6516 – 6521. Am. Chem. Soc. 2005, 127, 2565 – 2571.
[8] V. Percec, A. E. Dulcey, M. Peterca, P. Adelman, R. Samanta, V. S. K. Bala- [19] X. Zhu, A. Mourran, U. Beginn, M. Mçller, D. V. Anokhin, D. A. Ivanov,
gurusamy, P. A. Heiney, J. Am. Chem. Soc. 2007, 129, 5992 – 6002. Phys. Chem. Chem. Phys. 2010, 12, 1444 – 1452.
[9] X. Zhu, B. Tartsch, U. Beginn, M. Mçller, Chem. Eur. J. 2004, 10, 3871 – [20] R. I. Gearba, A. Bondar; M. Lehmann, B. Goderis, W. Bras, M. H. J. Koch,
3878. D. A. Ivanov, Adv. Mater. 2005, 17, 671 – 676.
[10] P. Oswald, P. Pieranski, Smectic and Columnar Liquid Crystals: Concepts [21] R. I. Gearba, D. V. Anokhin, A. I. Bondar, Y. K. Godovsky, V. S. Papkov,
and Physical Properties Illustrated by Experiments, Taylor & Francis, Boca N. N. Makarova, S. N. Magonov, W. Bras, M. H. J. Koch, F. Masin, B. Gode-
Raton, 2006. ris, D. A. Ivanov, Macromolecules 2006, 39, 988 – 999.
[11] Handbook of Liquid Crystals (Eds. D. Demus, J. Goodby, G. W. Gray, H. W. [22] R. I. Gearba, D. V. Anokhin, A. I. Bondar, W. Bras, M. Lehmann, D. A.
Spiess, V. Vill), Wiley-VCH, Weinheim, 1998. Ivanov, Adv. Mater. 2007, 19, 815 – 820.
[12] T. J. Dingemans, N. S. Murthy, E. T. Samulski, J. Phys. Chem. B 2001, 105, [23] R. I. Gearba, M. Lehmann, J. Levin, D. A. Ivanov, M. H. J. Koch, J. Baber,
8845 – 8860. M. G. Debije, J. Piris, Y. H. Geerts, Adv. Mater. 2003, 15, 1614 – 1618.
[13] T. J. Dingemans, L. A. Madsen, N. A. Zafiropoulos, W. Lin, E. T. Samulski, [24] W. Bras, I. P. Dolbnya, D. Detollenaere, R. van Tol, M. Malfois, G. N.
Philos. Trans. R. Soc. A 2006, 364, 2681 – 2696. Greaves, A. J. Ryan, E. Heeley, J. Appl. Crystallogr. 2003, 36, 791 – 794.
[14] V. Prasad, Sh.-W. Kang, K. A. Suresh, L. Joshi, Q. Wang, S. Kumar, J. Am.
Chem. Soc. 2005, 127, 17224 – 17227.
[15] R. A. Reddy, B. K. Sadashiva, V. A. Raghunathan, Chem. Mater. 2004, 16, Received: July 14, 2010
4050 – 4062. Published online on October 26, 2010
3644 www.chemphyschem.org 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2010, 11, 3638 – 3644