An oligooxamacrocycle containing a π-donor tetrathiafulvalene and a π-acceptor quinone. Molecular and supramolecular structure

Article abstract of DOI:10.1039/a705917e

Tetrathiafulvalenedicarbonyl chloride reacts with 2,5-bis[(2-hydroxyethoxy)ethyl]-1,4-benzoquinone to afford a novel charge-transfer oligooxamacrocycle whose molecular and supramolecular structure are reported.

Full text of DOI:10.1039/a705917e

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An oligooxamacrocycle containing a p-donor tetrathiafulvalene and a
p-acceptor quinone. Molecular and supramolecular structure
Robert M. Moriarty,*a Anping Tao,a Richard Gilardi,b Zhengzhe Songa and Sudersan M. Tuladhara
a Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60608, USA
b Naval Research Laboratory, 4555 Overlook Ave, Washington, DC 20375, USA
OH
S
S
S
S
Tetrathiafulvalenedicarbonyl chloride reacts with 2,5-bis[(2-
R
hydroxyethoxy)ethyl]-1,4-benzoquinone to afford a novel
OMe
charge-transfer oligooxamacrocycle whose molecular and
supramolecular structure are reported.
R
2a, R = H (TTF)
2b, R = CO2Me
2c, R = CO2H
2d, R = COCl
MeO
The p-donor charge transfer role of tetrathiafulvalene (TTF)
OH
(2a) as a molecular redox component is a key feature of organo-
1
electrochemical devices such as conducting and super-
conducting materials, sensors, molecular shuttles, NLO materi-
als, organic ferromagnets and C60-complexes.1 An important
structural feature in these materials is the spatial arrangement of
the TTF with respect to the p-acceptor unit, either a non-
covalent self-assembled array, or a covalently bonded system in
which the position of the interacting (charge transfer groups) is
fixed by synthetic design. Structures of increasingly evolved
synthetic design have been reported, notably, the synthesis of
tetrathiafulvalenoparacyclophanes and tetrathiafulvaleno-
phanes by Staab et al.,2 the joining of TTF-thiols by Hg2+ or
Ni2+,3 the incorporation of TTF into crown ethers,4 cages5 and
[3]-pseudocatenanes,6 the coupling of TTF to a ferrocenyl unit,7
and the incorporation of TTF into a dimacrocycle with a
catenated cyclobis(paraquat-p-phenylene).8 Incorporation of
TCNQ into a [2.2]paracyclophane has been accomplished;
however, the p-donor was not TTF but the essentially irrelevant
phenyl9 and 1,4-dimethoxyphenyl groups.10
i. N2CHCO2Et, BF3•OEt2, CH2Cl2 (28%)
ii. LiAIH4, THF (74%)
OH
O
OH
OH
O
O
OMe
AgO, HNO3
dioxane
(74%)
MeO
O
O
O
OH
3
4
2d, Et3N, CH2Cl2 (47%)
2d, Et3N, CH2Cl2 (7%)
OMe
O
CAN or
AgO
X
These molecules and others11 represent only partial solution
to the synthetic problem of fixing both the p-donor TTF and
p-acceptor within the same molecule. We now report the
synthesis of such a molecule as embodied in the oligooxamacro-
cycle 6 (Scheme 1).
O
O
O
O
O
MeO
O
O
O
O
O
S
S
S
S
S
S
S
S
O
O
O
Macrocycle 5 is a yellow crystalline material which could not
be oxidized to 6 using ceric ammonium nitrate (CAN) or AgO.
Charge transfer complex 6 is a black crystalline material.† The
UV-VIS spectrum of 6 in chloroform shows absorptions at 252,
285, 302, 314 and 424 nm. There is no difference in the UV-VIS
spectrum of 6 when measured as a film made by spin-coating
from chloroform solution. In the VIS-NIR range no absorption
5
6
Scheme 1
cell. However, the relationship between the second and the third
molecule is such that there are certain close atom contacts, but
the quinone and TTF of adjacent molecules do not
overlap. They are related by a different inversion centre [1.0 2
x, 1.0 2 y, 1.0 2 z]. Repeats of these operations produce an
oblique stack of pairs (dimers that possess quinone–TTF
overlaps) culminating in the depicted array of six stacks
(including solvent CHCl3) as shown in Fig. 3.
1
appears between 600–2500 nm. The position of the H NMR
chemical shift for the TTF portion in 6 is at 7.44 ppm compared
with 7.35 ppm for 2b. Likewise, the quinone hydrogen is at 6.65
ppm in 4 and 6.79 ppm in 6. The conductivity of a film of 6 (0.1
mm thick, 4 probe method) is s = 2.13 1025 S cm21, which
reveals the material to be a semiconductor.
The X-ray structure‡ of 6 may be discussed in terms of the
unit molecule 6 (Fig. 1), an arbitrary dimer and its stacking
(Fig. 2), and the supramolecular crystalline architecture (Fig. 3).
Fig. 1 shows the unit molecular structure. In agreement to
expectation, the quinone and TTF do not lie directly above and
below each other, although they do lie in parallel planes. The
distance between the centres of the non-overlapping quinone
and TTF is 6.869 Å. The quinone occupies a plane about 3.6 Å
above the extended parallel plane of the TTF. Fig. 2 shows a
stack of three pairs of ‘dimers.’ Each pair is composed of two
almost parallel planes of quinone and TTF. Going from the left
to the right of Fig. 2, the first two molecules of 6 nestle together
to afford partial overlap of TTF and quinone. These two are
related by a crystal inversion center [1.0 2 x, 1.0 2 y, z] in the
O7
O8
O4
O6
O3
S3
O1
S4
O2
S1
O5
S2
Fig. 1 X-Ray structure of the unit molecule 6
Chem. Commun., 1998
157

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TTF4
Larry L. Miller and Yoshihito Kunugi for measuring the
electrical conductivity and UV-VIS spectra.
TTF2
Q3
Q1
Footnotes and References
* E-mail: Moriarty@uic.edu
† The starting material 1 was prepared from 2,5-dihydroxy-benzene-
1,4-diacetic acid (J. H. Wood and R. E. Gibson, J. Am. Chem. Soc., 1949,
71, 393). 2d was prepared from carbon disulfide and methyl propiolate via
three steps (L. R. Melby, H. D. Hartzler and W. A. Sheppard, J. Org. Chem.,
1974, 39, 2456). Compound 6 was isolated from the reaction mixture by
filtration and purified by column chromatography.
‡ The crystalline compound 6 is monoclinic with space group P21/ c.
Parameters of the unit cell at 294 K: a = 10.8785, b = 26.237, c = 10.5339
Å, a = g = 90, b = 108.530°, V = 2850.7 Å3, Z = 4. Refinement method:
full-matrix least-squares on F2. Final R indices [I > 2s(I)]: R = 0.0491,
wR = 0.1080; R indices for all data: R = 0.1023, wR = 0.1284. CCDC
182/671.
Q4
Q2
TTF3
TTF1
Fig. 2 Stack of three dimers. Hydrogens and solvent (CHCl3) are removed
for clarity
0
b
1 T. K. Hansen and J. Becher, Adv. Mater., 1993, 5, 288.
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a
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Fig. 3 Six stacks viewed down the c axis of the unit cell. Solvent chloroform
is included in channels.
9 M. Yoshida, H. Tatemistu, Y. Sakata and S. Misumi, Tetrahedron Lett.,
1976, 3821.
10 H. A. Staab and H.-E. Henke, Tetrahedron Lett., 1978, 1955.
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The basic molecule 6 and higher oligooxa homologue tethers
of increasing –OCH2CH2O– units available by modification of
the synthetic route offer the interesting possibility of complexa-
tion of alkali metal ions. Finally, the design of 6 owes much to
the pioneering work of Staab and coworkers on oligooxapara-
cyclophane charge-transfer quinhydrones.12
Generous support of this work by the National Science
Foundation under grant CHE-9520157 is gratefully acknow-
ledged. We thank Nicholas Castellucci of Northrop Grumman
Co. for important advice and suggestions. We also thank Dr
Received in Corvallis, OR, USA, 13th August 1997; 7/05917E
158
Chem. Commun., 1998