I > 2s(I), wR2 = 0.2390 for all data, GoF = 1.040, Flack parameter
=
ꢁ0.07(6). CCDC 774704. Crystal data for (R)-1ꢀAgBF4:
C44H34AgBF4N4O4, M = 877.43, orthorhombic, space group P2221,
a = 8.2140(5), b = 13.8169(7), c = 41.563(2) A, U = 4717.1(5) A3,
Z = 4, Dc = 1.236 g cmꢁ3, m(Mo-Ka) = 0.484 mmꢁ1, F(000) = 1784,
final R1 = 0.0728 for I > 2s(I), wR2 = 0.2215 for all data,
GoF = 1.083, Flack parameter = 0.08(6).
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Fig. 4 The p–p stacking interaction involving bipyridine moieties
between two neighboring helices (a) and the lamellar structure formed
by electrostatic attraction as well as C–Hꢀ ꢀ ꢀF hydrogen bonding
ꢁ
between the cationic polymers and the BF4 anions (b) in crystalline
(S)-1ꢀAgBF4.
Fig. 5 Schematic representation of the hierarchical self-assembly of
(S)-1ꢀAgPF6 into gel nanofibers. (a) Molecule (S)-1, (b) nanotubular
P-helical polymers, (c) multilayers, (d) gel nanofibers, (e) gel formed
by (S)-1ꢀAgPF6.
The former two peaks were ascribed to the diffraction from
(002) plane constructed from 2D layers corresponding to a
layer thickness of 3.72 nm, and the diffraction from (100)
plane corresponding to a helical pitch, respectively. The
diffraction signal at d-spacing of 0.38 nm was ascribable to
p–p interactions between the bipyridine moieties. Interestingly,
the XRD patterns of other xerogels exhibited different inter-
layer distances and helical pitches (Fig. S11w), which were
evidently affected by the counterions. These results supported
the fact that the tubular helical coordination polymers
were preserved in the gels. Thereby, the stereoselective and
hierarchical self-organization processes of these supramolecular
gels could be reasonably deduced. The tubular homochiral
helical coordination polymer by chiral binaphthylbisbipyridine
ligands and silver(I) ions, the 2D layer by p–p interactions
between polymeric chains, and the nanofibers with the lamellar
structure by 2D layers, were formed step by step (Fig. 5).
In summary, we have successfully demonstrated the stereo-
selective and hierarchical self-assembly behaviors of a new
binaphthylbisbipyridine-based ligand and silver(I) ions from
nanotubular homochiral helical coordination polymers to
supramolecular gels. The counterions could change the
superstructures of the assemblies, such as the interlayer
distance and helical pitch. Incorporation of functional groups
into such nanotubular helical coordination polymers and their
application in enantio-selective recognition and separation are
currently underway.
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The work is supported by the National Natural Science
Foundation of China (20502024).
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Notes and references
z Crystal data for (S)-1ꢀAgBF4: C44H34AgBF4N4O4, M = 877.43,
orthorhombic, space group P2221, a = 8.2318(3), b = 13.8544(5),
,
c = 41.7301(16) A, U = 4759.2(3) A3, Z = 4, Dc = 1.225 g cmꢁ3
14 A. Westcott, C. J. Sumby, R. D. Walshaw and M. J. Hardie, New
J. Chem., 2009, 33, 902–912.
m(Mo-Ka) = 0.480 mmꢁ1, F(000) = 1784, final R1 = 0.0747 for
ꢂc
This journal is The Royal Society of Chemistry 2010
Chem. Commun., 2010, 46, 5695–5697 | 5697