Thiophene-coated functionalized M12L24 spheres: Synthesis, characterization, and electrochemical properties

Article abstract of DOI:10.1002/asia.201200413

Instant balls: Well-defined thiophene-coated functional nanospheres were synthesized by instantaneous self-assembly of twelve 90° Pd ^II-containing compounds and twenty-four 120° organic bidentate ligands in acetone. This solvent system was efficient to prepare the self-assembled complexes, facilitating isolation and purification. The self-assembled functional nanospheres exhibited interesting electrochemical properties. Copyright

Full text of DOI:10.1002/asia.201200413

DOI: 10.1002/asia.201200413
Thiophene-Coated Functionalized M12L24 Spheres: Synthesis,
Characterization, and Electrochemical Properties
Fei Jiang, Ning Wang, Zhengkun Du, Jun Wang, Zhenggang Lan, and Renqiang Yang*[a]
Precise self-assembly reactions to synthesize supramolec-
ular complexes and coordination polymers with novel struc-
tures and functional properties have attracted considerable
interests by chemists.[1,2] One big challenge of self-assembly
is to create well-defined nanoscale complexes with control-
lable sizes and shapes. In recent years, the coordination-
driven self-assembly method was proposed as a powerful al-
ternative technique to perform the efficient synthesis of
multifunctional molecules. For example, Stang and co-work-
ers reported a facile synthetic route to prepare snowflake-
Scheme 1. Self-assembly reaction in the preparation of spherical M12L24
shaped metallodendrimers with hexagonal cavities as their
complex 2 with 24-fold exterior surface appended with 2- or 3-substituted
cores.[1d] Fujita and co-workers succeeded in the self-assem-
thiophene functional groups.
bly of the first artificial sphere-in-sphere molecule.[2j] Thio-
phene-based molecules and polymers are great promising
functional materials for photovoltaic cells,[3,4] pharmaceuti-
cals,[5] and dyes.[6] However, traditional synthetic routes
often give low product yields and largely disordered struc-
tures of the thiophene derivatives. Meanwhile, functional
thiophene derivatives, especially those applied to supra-
molecular self-assembly, have hardly been reported. Stimu-
lated by these ideas, we envision that when the thiophene
functional group is attached at the vertex of a bidentate
ligand that is combined with an appropriately designed pal-
ladium(II)-containing compound, it will provide access to
a new family of multifunctional spherical structures. More-
over, this strategy allows us to control precisely the shape
and size of resulting spheres, the total number of incorporat-
ed functional moieties (thiophene), as well as the distribu-
tion of the above quantities.[7] The thiophene units hanging
outside of the spheres are the novel functional groups which
will make the self-assembled coordination systems exhibit
some unique electrochemical properties.
Scheme 1). Two different thiophene functional groups (2-
substituted or 3-substituted thiophene) were attached to the
1208 bidentate ligands, denoted as 1a and 1b, respectively.
Thus by linking a thiophene functional group at the vertex
of each bent bridging ligand, all 24 thiophene groups were
precisely appended outside of the spherical complexes.
From starting material 3,5-dibromophenol, bidentate ligands
1a and 1b were obtained with a relatively high yield
through four-step reactions (see the Supporting Information,
Scheme S1-S2). When ligand 1a (0.1 mmol in acetone) was
added into PdACHTNUGTRNEG(UN NO3)2 acetone solution (0.05 mmol,
0.5 equiv) at room temperature, the thiophene-appended
spherical complex 2a precipitated immediately. The reaction
process required simple mixing of metals (M) with ligands
(L) according to the 12:24 stoichiometric ratio. The self-as-
sembly reaction occurred so quickly that it was completed
within just a few seconds, and a rather high yield of 88%
was achieved. Such high reaction rates and yields can be ex-
plained by the different solubilities of reactants and prod-
Herein, we report an instant synthesis method to prepare
coordination spheres with an exterior surface featuring 24
thiophene functional groups. The shell of each coordination
sphere displayed a rigid and well-defined framework that
was assembled from twelve 908 metal-containing compounds
(M) and twenty-four 1208 organic bidentate ligands (L,
ucts. Both the metal precursor (PdACTHNUTRGNEUNG(NO3)2) and organic bi-
dentate ligands (1a and 1b) were well soluble in acetone,
whereas the resulting coordination spheres (2a and 2b)
were insoluble in acetone. Thus the reaction equilibrium
moved quickly towards the positive direction, and a high
yield of products was achieved within a very short time. Our
results indicated that the unique solvent system was very ef-
ficient to prepare the self-assembled complexes compared
to previously reported ones,[8] facilitating isolation and pu-
rification.
[a] F. Jiang, N. Wang, Z. Du, J. Wang, Prof. Dr. Z. Lan, Prof. Dr. R. Yang
Qingdao Institute of Bioenergy and Bioprocess Technology
Chinese Academy of Sciences
189 Songling Rd., Qingdao 266101 (China)
Fax : (+86)532-8066-2778
E-mail: yangrq@qibebt.ac.cn
The formation of a single product 2a was qualitatively
characterized by 1H NMR spectroscopic analysis (Fig-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200413.
1
ure 1b). Compared to ligand 1a, the H NMR spectrum of
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a single diffusion coefficient at 1.66ꢁ10À10 m2 sÀ1 (logD=
À9.78; Figure 1c). According to the Stokes–Einstein equa-
tion,[11] the diameter of sphere 2a was estimated to be
4.3 nm. Similarly, sphere 2b was assembled from 3-substitut-
ed thiophene ligand 1b and PdACHTNUGRTNEUNG(NO3)2. The diffusion coeffi-
cient in [D6]DMSO determined by DOSY experiment was
1.58ꢁ10À10 m2 sÀ1 (log D=À9.80), almost the same value as
for sphere 2a (see Figure S12 in the Supporting Informa-
tion). This result indicated that the two spheres (2a and 2b)
were nearly equal size, despite the different substitution po-
sitions in the thiophene ring.
The spherical structure of 2a was also ascertained directly
by AFM (Figure 2), which clearly showed that the spherical
complex 2a comprised 4–5 nm molecular particles. For both
2a and 2b, the sizes of the supramolecular nanospheres
were in agreement with those obtained from DOSY de-
duced results and theoretical calculations at the semi-empir-
ical PM6 level using Gaussian 09 package[12] (Figure 3 and
Figures S16 and S17 in the Supporting Information). The
structure of 2a and 2b was clearly a highly symmetric cu-
boctahedron structure, which may be viewed as a cube that
has every vertex truncated to generate eight triangular
faces. The theoretical calculations showed that the diameter
Figure 1. 1H NMR spectrum (600 MHz, [D6]DMSO, 298 K) of a) ligand
1a and b) sphere 2a; signals a, b, e, f, and g denote PyHa, PyHb, and 2-
substituted thiophene ring protons, respectively, while peaks c and d orig-
inate from the benzene ring. c) 1H DOSY spectrum of 2a (600 MHz,
[D6]DMSO, 298 K).
À
and the longest Pd Pd distance of sphere 2a were 4.8 nm
2a showed only one set of signals, in good agreement with
its highly symmetric spherical structure. The peak at
9.5 ppm was assigned to PyHa (peak a, Py=pyridinyl) and
the peak at 8.4 ppm was assigned to the superimposed PyHb
(peak b) and benzene proton (peak d), and peak c was as-
signed to the other two protons in the benzene ring. The
proton signals e, f, and g corresponded to the three types of
protons in the 2-substituted thiophene ring. The large down-
field shifts of signals on the a-
and 2.7 nm, respectively. Both of the spherical complexes
(2a and 2b) had 24 thiophene units equivalently appended
on the periphery of the spheres.
Similar synthetic ideas were employed to synthesize endo-
hedral thiophene-based functional ligands 1c and 1d
(Scheme 2) according to the same procedure as for 1a and
1b (see the Supporting Information and Scheme S4 for de-
tails). However, endohedral functional spheres were not ob-
site and b-site protons in the
pyridine group (e.g., Dd=
0.81 ppm and 0.54 ppm, respec-
tively) can be ascribed to strong
À
Pd N coordination interac-
tions.[9] The broadening of the
signals in the 1H NMR and
DEPT Q NMR spectra (Fig-
ure 1b and Figures S5,S6 in the
Supporting Information) re-
flects the slow dynamic motion
of the rigid large cores.[10] Simi-
lar results were obtained for
2b. Elemental analysis of 2a
and 2b provided further evi-
dence to support the formation
of current spherical structures
(see the Supporting Informa-
tion for details).
Diffusion-ordered
NMR
spectroscopy (DOSY) further
confirmed the selective forma-
tion of a single species. The
proton signals of 2a showed Figure 2. AFM images of 2a on mica, a) 3D image, b) 2D image, and c) height profile.
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Thiophene-Coated Functionalized M12L24 Spheres
Figure 3. Simulated molecular model of spheres 2a and 2b optimized at
the semi-empirical PM6 level using Gaussian 09 package.
Figure 4. a) The cyclic voltammograms of ligand 1b and sphere 2b at
a scan rate of 100 mVsÀ1, b) the cyclic voltammograms of sphere 2b at
scan rates of 50, 75, 100, 125, 150, 175 and 200 mVsÀ1, respectively. Solu-
tion: 7.2 mm 1b and 0.3 mm 2b in DMSO. Results are reported versus
Ag/AgCl. Inset: linear curve of the reduction current (ipc) versus the
square root of the sweep rate (v1/2).
Scheme 2. Molecular structures of ligands 1c and 1d.
tained. This result was probably due to steric repulsion be-
tween the pyridyl groups and the benzene rings.[13] For ex-
ample, ligand 1c perhaps adopted unfavorable nonplanar
conformation and did not assemble into the M12L24 complex
upon complexation with PdII compounds. Thus the four pyr-
idyl groups should display a perpendicular array with re-
spect to the PdN4 plane, which seems to be essential to the
self-assembly of the spherical complex.
200 mVsÀ1 (Figure 4b and inset). This finding indicated that
a diffusion-controlled redox process took place for sphere
2b. Similar results were obtained for sphere 2a (see Fig-
ure S13 in the Supporting Information). It is worth noting
that both 1a and 2a had larger reduction currents (ipc) than
1b and 2b, respectively, at the same concentration. For ex-
ample, the peak current (ipc) of sphere 2a was 4.562ꢁ
10À5 A, while the ipc of sphere 2b was 2.418ꢁ10À5 A at the
same concentration (0.3 mm). We deduced that the 2-substi-
tuted thiophene functional complexes can diffuse more
easily to the electrode than those with 3-substituted thio-
phene functional groups. Cyclic voltammograms of sphere
2a also showed a broad voltammetric peak, which probably
resulted from the multielectron transfer process that oc-
curred simultaneously. No decomposition of the complexes
during these redox processes was observed, as indicated by
the examination of the 1H NMR spectra of 2a and 2b
before and after the redox studies.
In summary, an instant self-assembly method was devel-
oped to synthesize well-defined spherical complexes, which
were assembled from twelve 908 metal subunits (M) and
twenty-four 1208 organic bidentate ligand subunits (L) in
acetone. The unique solvent system was confirmed as an ef-
ficient, simple method to prepare the self-assembled com-
plexes compared to previously reported ones, facilitating
isolation and purification. The spherical complexes have
been characterized by NMR spectroscopy, elemental analy-
The electrochemical properties of 24-fold spherical com-
plexes (2a and 2b) were investigated. To explore the role of
coordination effects, the voltammetric behaviors of sphere
2b and ligand 1b in DMSO were measured at concentra-
tions of 0.3 mm and 7.2 mm (24 equiv), respectively. Their
cyclic voltammograms were obtained in the potential range
from À2.0 to +2.0 V at a scan rate of 100 mVsÀ1. As shown
in Figure 4a, the reduction potential (Epc) of ligand 1b was
À1.212 V, and the reduction potential (Epc) of sphere 2b was
À1.059 V. In other words, the potential peak was positively
shifted by 0.153 V from 1b to 2b. We assumed that the posi-
tive shift was perhaps due to the cationic status of spheres
after coordination. However, the nearly identical peak cur-
rents (ipc) of ligand 1b and sphere 2b simply reflected the
similar numbers of 2-substituted thiophene moieties in 1b
and 2b, since the concentration of 2-substituted thiophene
functional groups in 1b (7.2 mm) was equivalent to that of
sphere 2b (0.3 mm). Sphere 2b showed only one broad re-
duction potential, indicating that no interaction existed
among the multiple redox centers at the periphery of the
sphere.[14] The reduction currents (ipc) of sphere 2b increased
linearly with the square root of the sweep rate from 50 to
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sis, AFM images, and theoretical calculations. DOSY NMR
spectroscopy, AFM images, and theoretical calculations con-
firmed the formation of nanoparticles with size 4–5 nm. The
hollow core environment provides an ideal cavity for guest
encapsulation. Meanwhile, the thiophene functional groups
were attached to the vertexes of each ligand, and the ob-
tained spherical complexes exhibited interesting redox prop-
erties. Moreover, the bulk properties of this type of novel
functional material can be tailored via the development of
spherical complexes decorated by other functional groups,
such as ferrocene, fluorene, and phthalocyanine moieties.
We expect that the combination of functional and encapsu-
lated moieties at the periphery and the interior of the
spheres, respectively, will allow such spherical molecules to
not only act as host “container compounds” but also possess
some electrochemical or photochemical applications, such as
multielectron redox catalysts, electrode modifiers, and sen-
sors.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (21103213, 51173199), the Ministry of Science and Technology of
China (2010DFA52310), CAS (“One Hundred Talented Program”, and
KGCX2-YW-399+9-2), the Department of Science and Technology of
Shandong Province (2010GGC10345), and the Qingdao Municipal Sci-
ence and Technology Program (11-2-4-22-hz). J.W. and Z.L. acknowledge
the computing resources in the super-computational center in QIBEBT
and SCCAS.
Keywords: electrochemistry · nanostructures · palladium ·
self-assembly · thiophene
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Thiophene-Coated Functionalized M12L24 Spheres
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Received: May 8, 2012
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Self-Assembly
Fei Jiang, Ning Wang, Zhengkun Du,
Jun Wang, Zhenggang Lan,
Renqiang Yang*
&&&& — &&&&
Thiophene-Coated Functionalized
M12L24 Spheres: Synthesis, Characteri-
zation, and Electrochemical Properties
Instant balls: Well-defined thiophene-
coated functional nanospheres were
synthesized by instantaneous self-
assembly of twelve 908 PdII-containing
compounds and twenty-four 1208
organic bidentate ligands in acetone.
This solvent system was efficient to
prepare the self-assembled complexes,
facilitating isolation and purification.
The self-assembled functional nano-
spheres exhibited interesting electro-
chemical properties.
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Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!