Redox-active tubular frameworks with TTF: Self-assemblies by complementary hydrogen-bonds and π-stacks of TTF-phenyluracil

Article abstract of DOI:10.1039/c1ce05794d

Tubular frameworks of a tetrathiafulvalene (TTF) based electron-donor with a N¹-phenyluracil moiety were constructed by strong self-assembling abilities. The uracil moiety formed the reversed Watson-Crick type hydrogen-bond pair. The TTF moiety

Full text of DOI:10.1039/c1ce05794d

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PAPER
Redox-active tubular frameworks with TTF: self-assemblies by
complementary hydrogen-bonds and p-stacks of TTF-phenyluracil†
Tsuyoshi Murata, Suguru Maki, Makoto Ohmoto, Eigo Miyazaki, Yoshikazu Umemoto, Kazuhiro Nakasuji
*
and Yasushi Morita
Received 25th June 2011, Accepted 19th August 2011
DOI: 10.1039/c1ce05794d
Tubular frameworks of a tetrathiafulvalene (TTF) based electron-donor with a N1-phenyluracil moiety
were constructed by strong self-assembling abilities. The uracil moiety formed the reversed Watson–
Crick type hydrogen-bond pair. The TTF moiety exhibited C–H/X hydrogen-bonds, S/S
interactions, and uniform p-stack. The phenyl group formed a herring-bone array by the edge-to-face
ꢀ
interaction. These multiple intermolecular interactions established channels of ca. 4 ꢀ 8 A. The cavities
were filled with crystalline solvent molecules (tetrahydrofuran and pyridine), which were fixed on the
framework by the C–H/X hydrogen-bonds.
skeleton are potential candidates for the multifunctional molec-
Introduction
ular conductors with guest inclusion–release behavior. Several
TTF-based tubular frameworks have been reported.8–10
However, in many cases, the frameworks are composed of
multiple components, and intermolecular interactions with
counterparts play a vital role in the formation of tubular struc-
tures.8 Except for the cyclic TTF derivatives (TTF-cyclophanes
and TTF-crown ethers),9 tubular frameworks composed of
a single component and formed only by the self-assembling
ability of the molecule are rare.10 The CT salts of diiodo(pyr-
azino)diselenadithia- and tetraselenafulvalenes with octahedral
counter-anions possess one-dimensional channels by the N/I
and p–p donor–donor interactions occupied by the counter-
anions.10
Porous compounds with one-dimensional tubular frameworks
established by noncovalent interactions can be used in a wide
range of applications such as selective molecular adsorption,
ion exchange, gas storage and as sensors by selective recogni-
tion of guest molecules in nanometre-sized cavities.1 The
investigations are most actively performed in self-assembled
coordination hosts and porous coordination polymers in view
of the high designability, surface functionality, flexibility and
dynamics of the frameworks originating from the appropriate
strength of the binding energy.2 In these studies, nitrogen-atom-
incorporated and/or carboxylic acid functionalized benzene
derivatives play a central role as organic parts of the frame-
works. Notably, these frameworks possess no or very weak
redox activity, and therefore strong charge-transfer (CT)
interactions between frameworks and guest molecules have
rarely been observed in the porous compounds.3,4 The intro-
duction of strong electronic interactions between frameworks
and guest molecules is expected to develop new functionalities
of porous compounds such as selective gas adsorption3,4 and
guest-dependent responses in the magnetic5 and transport
properties.6 From this viewpoint, much attention has recently
been focused on redox-active porous compounds.3,4
A precise control of molecular arrangements of TTF skele-
tons by directional intermolecular interactions, such as
hydrogen-bonds (H-bond),11–13 is one of the powerful tools in
constructing TTF-based tubular frameworks. We have studied
butyluracil-functionalized TTF derivatives (1) exhibiting a self-
assembling ability by the complementary H-bonds as well as p-
stacks and S/S contacts on the TTF skeleton.14 In the CT
complex of 1b with TCNQ (tetracyanoquinodimethane), the
self-assembling ability of 1b demonstrated a TTF-based one-
dimensional tubular framework, in which the TCNQ guest
stacked one-dimensionally along the host channel.14b The host
channel was formed between the self-assembled donor-layers,
Tetrathiafulvalene (TTF), a strong electron-donor widely
studied in the research field of organic conductors, exhibits stable
radical cation species.7 Porous compounds formed by the TTF
Department of Chemistry, Graduate School of Science, Osaka University,
Toyonaka, Osaka, 560-0043, Japan. E-mail: morita@chem.sci.osaka-u.ac.
jp; Fax: +81-6-6850-5395; Tel: +81-6-6850-5393
† Electronic supplementary information (ESI) available: atomic
numbering schemes and overlap modes in the crystal structures. CCDC
reference numbers 826938 & 826939. For ESI and crystallographic data
in CIF or other electronic format see DOI: 10.1039/c1ce05794d
6880 | CrystEngComm, 2011, 13, 6880–6884
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and each channel was separated by the butyl groups. The
intermolecular interactions between donor-layers were not
observed, and the one-dimensional stack of the TCNQ guest
also contributed to the construction of this tubular framework.
Actually, a tubular framework was not observed in the crystal
structures of neutral 1a and 1b where the butyl group was only
located in the space between TTF and uracil moieties.14 For the
TTF-based tubular frameworks, we have designed a phenyl-
uracil-substituted TTF 2 to introduce interlayer interactions
into TTF-uracil crystals. The benzene ring forms a herring-
bone array by the edge-to-face (C–H/p) interaction as seen in
the crystal structure of benzene.15 Here we have demonstrated
one-dimensional tubular frameworks, which were formed by
the complementary H-bonds on the uracil moiety, p-stacks and
S/S contacts on the TTF moiety, and edge-to-face interaction
on the phenyl group.
Fig. 1 IR spectra of 1a and 2 in KBr pellets and two types of comple-
mentary H-bonds of the uracil moiety in each compound.
was preserved in both the 2$THF and 2$pyridine crystals (vide
infra).
Results and discussion
Synthesis and electrochemical properties
Crystal structure of 2$THF
Synthesis of 2 was carried out by the Stille cross-coupling
reaction of tributylstannyl-substituted TTF with 5-iodo-1-phe-
nyluracil in the presence of Pd(PPh3)4. The redox potentials of
In the crystal of 2$THF, the TTF skeleton had a nearly planar
structure with bent angles of 4.0ꢂ, and the uracil moiety was
nearly parallel to the TTF skeleton with a dihedral angle of
5.4ꢂ. The phenyl group was largely inclined to the uracil moiety
by 62.7ꢂ due to the steric repulsion of the C]O group. Two
donor molecules interacted through the reversed Watson–Crick
2 with two-stage reversible one-electron oxidation (Eox1
¼
ꢁ0.08; Eox2 ¼ +0.17 V vs. Fc/Fc+) are closely similar to those of
pristine TTF (Eox1 ¼ ꢁ0.08; Eox2 ¼ +0.16 V) and 1a (Eox1
¼
ꢁ0.08; Eox2 ¼ +0.14 V), indicating the strong electron-donating
ability of 2. Recrystallization by the vapour diffusion method
using THF– or pyridine–hexane gave solvated crystals, 2$THF
or 2$pyridine, respectively.‡ These crystals were stable in the
crystallization solvent. However, when the crystals were
exposed to the atmosphere or were soaked in poor solvents
(hexane, etc), they gradually collapsed due to the release of the
guest molecules.
ꢀ
type H-bonds (N/O distance, 2.87 A) on the uracil moiety to
form a dimer (Fig. 2a). Moreover, the dimer assembled along
the [201] direction through the weak C–H/S H-bond (C/S
ꢀ
distance, 3.66 A) on the TTF moieties, which is known as an
important interaction controlling the molecular packing of CT
complexes and salts.12,18 The TTF moiety formed a slipped p-
stacking motif and
a uniform column along the b-axis
(Fig. 2b).† These interactions on the uracil and TTF moieties
formed a two-dimensional donor-layer. The phenyl group on
the uracil moiety formed a herring-bone array by the edge-to-
Vibration spectra: prediction of H-bonding mode
ꢀ
For uracil derivatives, C]O stretching modes (nC]O) in the IR
spectra are known to be probes for the identification of their
complementary H-bond types (Fig. 1) from experimental and
theoretical studies.16 The butyluracil derivative 1a forming
Watson–Crick type H-bonds (C4 ¼ O/H–N3, Fig. 1)13a shows
two nC]O modes at 1702 and 1655 cmꢁ1 which are assigned as
C2 ¼ O and C4 ¼ O modes, respectively. While, 2 shows a single
nC]O mode at 1697 cmꢁ1, suggesting the reversed Watson–Crick
type H-bonds (C2 ¼ O/H–N3, Fig. 1), which has been rarely
observed in several uracil derivatives.17 This H-bonding type of 2
face interaction (C–H/p distance, 2.81 A) parallel to the p-
stacks of TTF skeleton (Fig. 2c). The TTF-uracil layers were
connected by these edge-to-face interactions and the C–H/O
contact between phenyl and carbonyl groups of the uracil
ꢀ
moieties (C/O distance, 3.24 A) (Fig. 2a). These robust and
weak intermolecular interactions established a one-dimensional
ꢀ
porous structure with a rectangular cavity of ca. 4 ꢀ 8 A size
(Fig. 3). Walls of the tubular framework were composed of
herring-bone arrays of the phenyl group and one-dimensional
stacks of the TTF moiety which tilted by ca. 40ꢂ with respect to
the tube direction. The THF guests were fixed to the cavity by
C–H/O weak H-bonds with the uracil and phenyl moieties
‡ Crystallographic data for 2$THF: C18.98H15.96N2O2.75S4, M ¼ 443.90,
monoclinic, space group P21/c (no. 14), a ¼ 18.863(8), b ¼ 5.722(3), c
ꢀ
(C/O distances, 3.55 and 3.43 A, respectively) (Fig. 2a
and 2c).
ꢂ
3
ꢀ
ꢀ
¼ 21.510(9) A, b ¼ 116.96(3) , V ¼ 2069(2) A , Z ¼ 4, Dc ¼ 1.425 g
cmꢁ3, l ¼ 0.71075 A, m(Mo-Ka) ¼ 4.80 cmꢁ1, F(000) ¼ 918.5, T ¼ 200
ꢀ
K, 2qmax ¼ 55.0ꢂ, 4269 unique reflections of 15 488 collected (Rint
¼
0.058), R1 ¼ 0.069 and Rw ¼ 0.203 [I > 2.0s(I)], S(GOF) ¼ 1.03.
Crystallographic data for 2$pyridine: C21H15N3O2S4, M ¼ 469.60,
monoclinic, space group C2/c (no. 15), a ¼ 35.208(2), b ¼ 5.6195(3), c
Crystal structure of 2$pyridine
The 2 molecule in this crystal had a nearly planar TTF-uracil
skeleton and a large dihedral angle between the uracil and
phenyl moieties (64.0ꢂ) as shown in the 2$THF. Similar to
2$THF, two donor molecules in 2$pyridine formed a dimer by
ꢂ
3
ꢀ
ꢀ
¼ 25.610(2) A, b ¼ 126.721(2) , V ¼ 4061.5(5) A , Z ¼ 8, Dc ¼ 1.536 g
cmꢁ3, l ¼ 0.71075 A, m(Mo-Ka) ¼ 4.93 cmꢁ1, F(000) ¼ 1936, T ¼ 200
ꢀ
K, 2qmax ¼ 54.9ꢂ, 4638 unique reflections of 17 165 collected (Rint
¼
0.140), R1 ¼ 0.069 and Rw ¼ 0.111 [I > 2.0s(I)], S(GOF) ¼ 0.98.
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Fig. 2 Crystal structure of 2$THF. (a) The cavity formed by comple-
mentary N–H/O and weak C–H/X H-bonds viewed along the b-axis. (b)
The c-axis projection of a TTF-uracil layershowingtheone-dimensional p-
stacks of 2 molecules. (c) The herring-bone array of the phenyl group
together with the interacting THF solvent molecules. TTF and uracil
moieties are omitted for clarity (only N1 atom is remained). Red and blue
dotted lines show N–H/O and C–H/X (X ¼ O, S) H-bonds, respectively.
The gray double head arrows show the edge-to-face interaction of the
phenyl group. Ellipsoids are drawn at the 30% probability level.
Fig. 4 (a) Crystal structure of 2$pyridine. (a) The cavity formed by
complementaryN–H/OandS/Sinteractionsviewedalongtheb-axis. (b)
The TTF-uracil layer viewed along perpendicular to the molecular short
axis showing the one-dimensional p-stacks of the 2 molecules. (c) The
herring-bone array of the phenyl group together with the interacting
pyridine solvent molecules. TTF and uracil moieties are omitted for clarity
(only N1 atom is left). Green, red, and blue dotted lines show S/S contacts,
and N–H/O and C–H/X (X ¼ O, N) H-bonds, respectively. The gray
double head arrows show the edge-to-face interactions of the phenyl group
and pyridine. Ellipsoids are drawn at the 30% probability level.
skeletons inclined by ca. 80ꢂ, forming a one-dimensional chain
ꢁ
along the [101] direction (Fig. 4b). The TTF moiety uniformly
ꢀ
stacked with a slipped manner (3.55 A) along the b-axis to form
a TTF-uracil two-dimensional layer (Fig. 4b). The herring-bone
array of the phenyl groups by the edge-to-face interaction (C–
ꢀ
H/p distance, 3.01 A) was formed between the TTF-uracil
layers as observed in the crystal structure of 2$THF (Fig. 4a
and 4c). These interactions constructed a one-dimensional
ꢀ
porous structure with a cavity of ca. 4 ꢀ 8 A size (Fig. 5). The
cavity of the crystal was filled with pyridine molecules. Inter-
Fig. 3 A perspective view of the porous structure of 2$THF along the b-
estingly, pyridine guests interacted with the 2 hosts through
weak H-bonds with the uracil (C2 ¼ O/H–C, 3.43 A) and
axis.
ꢀ
ꢀ
ꢀ
the double complementary H-bonds (N/O distance, 2.89 A) of
the reversed Watson–Crick type (Fig. 4a). The dimers were
TTF moieties (C–H/N, 3.44 A), and through the edge-to-face
ꢀ
interaction with the phenyl group (C–H/p distance, 2.69 A)
(Fig. 4a and 4c).
ꢀ
connected via S/S contacts (3.50 A), where adjacent TTF
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(1.6 M hexane solution, 0.79 mL, 1.27 mmol) at ꢁ78 ꢂC and
stirred at this temperature for 1 h. Bu3SnCl (0.34 mL, 1.27 mmol)
was added to this mixture, and the reaction mixture was gradu-
ally warmed up to room temperature over 1.5 h. To the resulting
mixture was added a pH 7.0 phosphate buffer solution (0.1 M, 7
mL). The organic layer was separated, and the aqueous layer was
extracted with ethyl acetate (30 mL ꢀ 3). The combined organic
extracts were dried over Na2SO4, then filtered and concentrated
under reduced pressure. The residual oil was dried in vacuo at
room temperature, to give Bu3Sn-substituted TTF as an orange
oil. 5-Iodo-phenyluracil (400 mg, 1.27 mmol) and Pd(PPh3)4
(150 mg, 0.13 mmol) were placed in a Schlenk-tube equipped
with a reflux condenser, then a solution of Bu3Sn-substituted
TTF (660 mg) in DMF (15 mL) was added, and the resulting
Fig. 5 A perspective view of the porous structure of 2$pyridine along the
b-axis.
ꢂ
mixture was stirred at 100 C for 14 h. After cooling to room
temperature, a pH 7.0 phosphate buffer solution (0.1 M, 15 mL)
was added to the reaction mixture. The brown precipitate was
collected by filtration and washed with minimum amounts of
THF, to give 2 (195 mg, 39%) as an orange solid, (dried at room
temperature for 2 day): mp 274–275 ꢂC (dec); TLC Rf 0.20 (1 : 1
hexane–ethyl acetate); 1H NMR (DMSO-d6) d 6.73 (s, 2H), 7.37
(s, 1H), 7.43–7.54 (m, 5H), 7.75 (s, 1H), 11.85 (brs, 1H); EI-MS,
m/z 390 (M+, 78%); IR (KBr) 3435, 1697, 1430 cmꢁ1; UV (KBr)
428, 300 nm; Anal. Calcd for C16H10N2O2S4: C, 49.21; H, 2.58;
N, 7.17%. Found: C, 49.49; H, 2.81; N, 6.78%. Due to the strong
efflorescence nature, elemental analysis and optical measurement
of the solvent-including crystals could not be performed.
Conclusions
In summary, we demonstrated two kinds of crystal structures
showing one-dimensional tubular frameworks with phenyluracil-
functionalized TTF walls. These self-assembled architectures
were achieved by multiple intermolecular interactions; comple-
mentary H-bonds on the uracil moiety, weak C–H/X (X ¼ N,
O, S) H-bonds, S/S contacts, and p-stacks on the TTF skeleton,
and edge-to-face interactions on the phenyl group. The coexis-
tence of one-dimensional p-stacking columns and a one-dimen-
sional cavity filled with small molecules encourages us to explore
multifunctional organic conductors exhibiting inclusion
phenomena. The guest-exchange experiment of the porous
crystals of 2 with electron-acceptors (TCNQ, etc) in a poor
solvent for 2 is in progress for conductive porous CT complexes.
Electrochemistry
Cyclic voltammetric measurement was made with an ALS
Electrochemical Analyzer model 630A. Cyclic voltammogram
was recorded with 1.6 mm diameter gold plated carbon and Pt
wire counter electrodes in dry DMF containing 0.1 M Bu4NClO4
as supporting electrolyte at room temperature. The experiment
employed a Ag/AgNO3 reference electrode, and the final result
was calibrated with a ferrocene/ferrocenium couple.
Experimental
Materials and measurements
5-Iodo-phenyluracil was prepared according to our previous
paper.14b All reactions requiring anhydrous conditions were
performed under an argon atmosphere. Solvents were dried
(drying reagent in parenthesis) and distilled under an argon
atmosphere prior to use: THF (Na–benzophenone ketyl); DMF
(CaH2). The Rf value on TLC was recorded on E. Merck pre-
coated (0.25 mm) silica gel 60 F254 plates. The plate was sprayed
with a solution of 10% phosphomolybdic acid in 95% ethanol
and then heated until the spots became clearly visible. The
melting point was measured with a hot-stage apparatus and
X-ray crystallography
X-ray crystallographic measurements were made on a Rigaku
Raxis-Rapid imaging plate with graphite monochromatic Mo-
Ka radiation. An empirical absorption correction was applied
which resulted in transmission factors ranging from 0.744 to
0.972 for 2$THF and from 0.827 to 0.990 for 2$pyridine.
Structures were determined by a direct method using SHELXS-
97.19 Least-squares refinements were performed on F2 with
SHELXL-97.20 All non-hydrogen atoms were refined aniso-
tropically. Positional parameters of hydrogen atoms were
calculated with sp2 or sp3 configuration of the bonding carbon
and nitrogen atoms, and hydrogen atoms were refined using the
riding model. In the refinement procedures, isotropic tempera-
ture factors with magnitudes of 1.2 times of the equivalent
temperature factors of the bonding atoms were applied for
hydrogen atoms. A restraint for the C–C and C–O bond lengths
in the THF molecule was applied in the refinement. Furthermore,
the refinement was performed with a calculation of site-occu-
pancy factor of THF molecule and with a global Uiso value for
O3 and C17–C20 atoms.
1
uncorrected. H NMR spectrum was obtained on a JEOL EX-
270 with DMSO-d6 using Me4Si as an internal standard. EI-Mass
spectrum was taken at 70 eV by using a Shimadzu QP-5000 mass
spectrometer. The infrared spectrum was recorded on a JASCO
FT/IR-660 Plus spectrometer using a KBr plate (resolution
4 cmꢁ1). The electronic spectrum was measured by a Shimadzu
UV-3100PC spectrometer using a KBr plate. Elemental analysis
was performed at the Graduate School of Science, Osaka
University.
Synthesis of 4-(1-phenyl-2,4-pyrimidinedione-5-yl)-1,3-dithiole-
2-ylidene (2)
TTF (259 mg, 1.27 mmol) was placed in a Schlenk-tube and
dissolved with THF (7 mL). To this mixture was added n-BuLi
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ꢂ
ꢂ
3158; (c) K. Heuze, M. Fourmigue, P. Batail, E. Canadell and
P. Auban-Senzier, Chem.–Eur. J., 1999, 5, 2971; (d) T. Matsumoto,
Y. Kamada, T. Sugimoto, T. Tada, S. Noguchi, H. Nakazumi,
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8638.
Acknowledgements
This work was partly supported by Grants-in-Aid for Scientific
Research (20550051) and Challenging Exploratory Research
(21655015) from the Japan Society for the Promotion of Science,
and for Scientific Research on Innovative Area (20110006) and
Elements Science and Technology Project from the Ministry of
Education, Culture, Sports, Sciences and Technology, Japan.
9 Tubular frameworks based on the TTF-cyclophanes and TTF-crown
ethers, see: (a) K. B. Simonsen, N. Svenstrup, J. Lau, N. Thorup and
J. Becher, Angew. Chem., Int. Ed., 1999, 38, 1417; (b) F. Le Derf,
ꢂ
M. Mazari, N. Mercier, E. Levillain, G. Trippe, A. Riou,
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ꢂ
ꢂ
A. Gorgues and M. Salle, Chem.–Eur. J., 2001, 7, 447.
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(a) T. Imakubo, T. Maruyama, H. Sawa and K. Kobayashi, Chem.
Commun., 1998, 2021; (b) T. Imakubo, M. Kibune, H. Yoshino,
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11 Recent overviews of supramolecular assemblies based on H-bond: (a)
G. R. Desiraju and T. Steiner, The Weak Hydrogen Bond, Oxford
University Press, New York, 1999; (b) M. Alajarin, A. E. Aliev,
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12 Comprehensive review of H-bonded TTF derivatives, see:
Notes and references
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4 The weak CT interaction between ligand of the host and guest were
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ꢁ
AuCl4 as guests generate Ag and Au nanoparticles, see: (c)
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6884 | CrystEngComm, 2011, 13, 6880–6884
This journal is ª The Royal Society of Chemistry 2011