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diffraction pattern of cis-2, the main diffraction peak appeared as one
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[23] This diameter was estimated from the PM3 optimized structure of the
cis-azodibenzoic acid tetramer (Æ 2.31nm) onto which were super-
imposed four optimized decyloxy-substituted monomers. The distance
between two opposite chain-ends was measured directly. See Sup-
porting Information.
À
Phys. 1993, 98, 5648 5652; d) the C N N angle obtained by our
PM3 calculations for cis-p-azodibenzoic acid (126.98), cis-o-bis(me-
thoxy)-p-azodibenzoic acid (127.28), cis-o-bis(decyloxy)-p-azodiben-
zoic acid (127.88) agrees with experimental X-ray results for o-
substituted cis-azobenzene (126.48) (see ref. [20]). The details of these
calculations will be published elsewhere.
[14] See Supporting Information.
[15] Similar PM3 calculations were performed on hydrogen-bonded iso-
phthalic acid aggregates. These theoretical studies agree with exper-
imental evidence, showing that the unsubstituted isophthalic acid form
tapes instead of rosettes (see ref. [3a,b]), thus validating our pre-
dictions.
[16] Attempts to form cyclic cis-azodibenzoic acid trimers by using PM3
only yielded the open aggregates. A triangle was obtained from HF/
STO-3G monomers, which were then assembled to form the desired
structure, then optimized using PM3. This optimization gave a triangle
with bent hydrogen-bonds, which were weaker than in the larger
macrocycles and in the open aggregates.
[24] At very low concentrations (c <3 gLÀ1), the VPO data points lie
slightly below the regression curves, suggesting the preponderance of
monomeric species in such dilute solutions (See Supporting Informa-
tion). However, at higher concentrations, the results are consistent
with supramolecular tetramers.
À
[25] On the micrographs, the Pt C is seen as dark gray and the carbon as
light gray. For the replicas, the error estimate on the measurements is
Æ1nm. (see Supporting Information for details). However, the cis-2
isomer is expected to form hydrogen-bonded macrocycles in the solid
state as reflected by our XRD and TEM results.
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[26] The total energy of stacked supramolecular structures was computed
as a function of their inter-planar distance, the tilt of the aromatic rings
with respect to the normal to the macrocycle plane, and the horizontal
offset between the stacked macrocycles. The optimum structure
obtained by using the MM force field was further optimized using
PM3, leading to a very similar structure. Moreover, PM3 calculations
on cis-o-bis(alkyl)azodibenzoic acid predict that the alkyl chains are
able to adopt an orientation parallel to the azodibenzoic acid plane,
thus enabling the hydrogen-bonding and stacking interactions to
occur. As
a
result, PM3 and MM calculations show that the
orientation of the aromatic rings in the macrocycle and the position
of the alkoxy chains can favor the efficient stacking of these tetrameric
macrocycles into rod-like morphologies. The details of these calcu-
lations will be published elsewhere.
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[27] See Experimental Section for details.
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≈
0.03 mm, unit cell: triclinic, P1, a 8.3795(2), b 13.4914(3), c
15.1038(4) ä, a 105.732(2), b 94.757(2), g 91.273(2)8, V
1636.10(7) ä, 1calcd 1.183 gcmÀ3, qmax 72.79, CuKa, l 1.54178 nm,
collection method: phi scans, T 293 K, 19813 measured reflections,
6258 independent reflections, 3029 observed reflections, maximum
shift 0.021, absorption correction type multi scan, structure sol-
ution by direct method using SHELXS97, structure refinement using
SHELXL96, 383 parameters, isotropic hydrogen atoms using defaults,
R1 0.0626, wR2 0.1750, refinement against jF2 j . CCDC-184609
contains the supplementary crystallographic data for this paper. These
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¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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