New π-extended donors: Synthesis, characterization, electrochemical and electrical conductivity studies

Article abstract of DOI:10.1080/10426507.2010.530899

A new series of tetrathiafulvalene (TTF) molecules with extended π-system was prepared by using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of thiolates provided access to a wide variety of molecules. The study of the

Full text of DOI:10.1080/10426507.2010.530899

Phosphorus, Sulfur, and Silicon, 186:1744–1754, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.530899
NEW π-EXTENDED DONORS: SYNTHESIS,
CHARACTERIZATION, ELECTROCHEMICAL
AND ELECTRICAL CONDUCTIVITY STUDIES
Amel Zitouni, Abdelkrim Gouasmia, Sabrina Bouguessa,
Lakhe´mici Kaboub, and Louiza Boudiba
Laboratoire des Mate´riaux Organiques et He´te´rochimie, Universite´ de Te´bessa,
Te´bessa, Algeria
A new series of tetrathiafulvalene (TTF) molecules with extended π-system was prepared by
using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of
thiolates provided access to a wide variety of molecules. The study of their reducing power
was carried out by cyclic voltammetry. Charge transfer complexes have also been chemically
prepared by using TCNQ as an electron acceptor; the electrical conductivity of their compressed
powders shows insulator behavior. The IR spectra of the TCNQ salts were recorded and used
to characterize and estimate the degree of charge transfer of these complexes.
Keywords Cyclic voltammetry; π-extended electron-donors; organic materials; phosphonate;
phosphonium salt; thiolate
INTRODUCTION
The main objective of the current research in the field of the tetrathiafulvalenes aims
at the stabilization of the metallic state1,2 of the material resulting via the increase of their
dimensionality.3,4 To achieve this purpose, numerous tracks were developed, passing by
the preliminary modification of the skeleton of the tetrathiafulvalene (TTF). Among these
modifications are the multiplication of heteroatoms5–9 within the donor, and the introduction
of the combined systems more widened to limit the coulomb repulsion and strengthen the
coverings of orbital inter- and intrachains in the resultant material.10–13 In these optics, we
focused on the synthesis and solution redox properties at a new series of π-donors, in which
1,3-dithiole ring frameworks are attached to the periphery of TTF (Figure 1).
Received 13 July 2010; accepted 6 October 2010.
This work was realized within the framework of an agreement schedule Franco-Algerian of inter-university
cooperation (University of Te´bessa, University of Montpelier and University of Rennes) with the support of the
CMEP, the Algerian Ministry of Higher Education, and the French Ministry of Foreign Affairs, which we thank
sincerely.
Address correspondence to Abdelkrim Gouasmia, Laboratoire des Mate´riaux Organiques et He´te´rochimie,
Universite´ de Te´bessa, 12000 Te´bessa, Alge´rie (Algeria). E-mail: akgouasmia@hotmail.com, akgouasmia@univ-
tebessa.dz
1744

NEW π-EXTENDED DONORS
1745
S
S
S
S
S
SR
S
Me
Me
R= (CH2)2CN, CH3, R=R= CH2, (CH2)2, (CH2)3
Figure 1 π-Extended electron donors.
RESULTS AND DISCUSSION
The retro synthetic analysis of the key molecule 3 creates as a way of possible
synthesis a classical Wittig type reaction.14–16 Such a reaction can be realized between
two entities: a phosphonium salt and an aldehyde function introduced on a TTF unit. The
implementation of these syntheses requires the preliminary preparation of the appropriate
key molecules 1a, 1b, and 1c (Scheme 1).
S
S
S
S
S
S
Me
Me
S
CN
CN
3
Me
Me
S
S
S
S
H S
BF4 Ph3P
O
CN
CN
2
S
Me
S
S
1c
triMeTTF 1
2-
S
S
(nBu4)
S
Zn
2
Me
Me
S H
S
S
S
H
N
S PO(OMe)2
S
Me
PF6
1a
1b
Scheme 1
The first key starting material 1a (Scheme 2) was prepared in one step. Thus, 1.2
equiv. of freshly distilled trimethyl phosphite, in the presence of sodium iodide, were added
to a solution of one equivalent of dithiolium salts in anhydrous acetonitrile. The mixture
was maintained overnight under nitrogen at room temperature. After evaporation of the
solvent, the residue was taken back in ether, to give 2-dimethoxyphosphoryl-4,5-dimethyl-
1,3-dithiole as red oil in high yield (83%).
S H
S H
BF4
NaI, P(OMe)3
ACN, reflux
S PO(OMe)
S
1a 83%
Scheme 2

1746
A. ZITOUNI ET AL.
The second key intermediate compound 1b (Scheme 3) was prepared in two steps.
Thus, the (2-oxopropyl)-N,N-pentamethylenedithiocarbamate was prepared by a conve-
nient one flask reaction in which carbon disulfide was treated with piperidine to produce
piperidinium piperidinocarbo-dithioate. Without the isolation of this intermediate, the re-
action mixture was allowed to react with bromoacetone in ethanol at 80◦C. The solution
was usually left for 4–6 h to assure complete reaction. The resulting oxoesters are crys-
talline, colorless solids, and can be recrystallized from ethanol. The ring closure of the
oxoester was found to proceed smoothly in concentrated sulfuric acid. The hydrosulfates
obtained were converted to hexafluorophosphates by treating the reaction mixture with ex-
cess hexafluorophosphoric acid. The obtained 2-(N,N-pentamethylenimino)-1,3-dithiolium
salts are colorless crystalline compounds (75%).
O
NCS
BrCH2COCH3
EtOH, 80°C
NCSCH2COCH
H2N
H2SO4
O°C
Me
S
HBF4
BF4
N
1b 75%
Scheme 3
The third key intermediate 1c (Scheme 4), was in turn prepared in a five-step synthetic
procedure.18 In the first step of the process, the thione derivative was easily synthesized
in acetone by alkylation of TBA2[Zn(DMIT)2] bis(tetrabutylammonium) bis(1,3-dithiole-
2-thione-4,5-dithiolate zincate with 3-bromopropionitrile. S-Methylation of the thione was
performed by using methyl trifluoromethanesulfonate and tetrafluoroboric acid to give the
expected dithiolium cation salt. Reduction of the dithiolium salt with borohydride led to the
thioether. This latter compound was treated with tetrafluoroboric acid followed by addition
of triphenylphosphine to afford the corresponding 4,5-bis(2-cyanoethylthio)-1,3-dithiole-
2-triphenylphosphonium tetrafluoroborate in good yield (94%).
S
S
S
S
S
S
S
BrCH2CH2CN
ACN, N2, 80°C
S
S
Zn
S
(nBu4)2
RS
S
S
1)CF3SO3CH3
2)HBF4, CH2Cl2
RS
S H
RS
RS
S H
HBF4
Ether
RS
S
NaBH4
+
SMe, BF
RS
S SMe
iPrOH
S PPh BF
1c 94%
Scheme 4
The synthetic key step (Scheme 5) involves a Wittig–Horner reaction17,19 of the
phosphonate anions derived from reagent 1a. Imminium salt 1b reacted cleanly with the

NEW π-EXTENDED DONORS
1747
S H
S
S
Me
H
+
N
PF6
S PO(OMe)2
Me
1b
1a
1) THF, -78°C, N2, tBuOK
2) AcOH, Toluene, ACN
Me
H
S
S
S
S
1 60%
Scheme 5
anion followed by treatment, at room temperature, with a large excess of acetic acid allowed
to obtain the trimethyltetrathiafulvalene (triMeTTF) 1, with 60% yield.
One equivalent of N-methyl-N-phenylformamide was added to a lithiated TTF so-
lution in dry THF (Scheme 6), prepared earlier from triMeTTF (1 equiv.) and lithium
diisopropylamide (1.5 equiv.) at −78◦C. The reaction mixture was stirred at −78◦C for 1
h and then slowly warmed to room temperature over 12 h. The solution was acidified with
HCl (2N). After workup, the desired product 2 was obtained with 44% yield.
S
S
S
S
Me
Me
H
S
S
S
S
THF, -78°C, N , LDA
2
Me
M
Me
1
THF, -78°C, PhMeNCHO,
H20, HCl
Me
S
S
O
2 44%
Scheme 6
Construction of the π-extended TTF framework 3 from compound 2 was accom-
plished in two steps (Scheme 7). The phosphorus ylides generated by deprotonation of
reagent 1d20 (t-BuOK, −78◦C, ACN) reacted with aldehyde 2 to yield the highly conju-
gated π-electron donor systems21 with 83% yield.
Compound 3 represents a particularly versatile TTF derivative, as further functional-
ization of the thiolate anions can be readily achieved by the double deprotection,22 followed
by addition of an electrophile. Accordingly, TTF 3 (Scheme 8) was reacted with two equiv-
alents of sodium ethoxide in ethanol to remove two cyanoethyl groups. The resulting
dithiolate species was then reacted in situ with either methyl iodide, dibromomethane,
1,2-dibromoethane, or 1,3-dibromopropane to afford the expected known products 4a–d
(52–83% yield).
The donor ability of compounds 3 and 4a–d was studied by cyclic voltammetry
(CV). All measurements were performed on platinum working and counter electrodes in
dry CH2Cl2 at room temperature containing 0.1 M n-Bu4NBF4 as the supporting electrolyte
and with a SCE reference electrode. A scan rate of 100 mV s−1 was used.

1748
A. ZITOUNI ET AL.
S H
S
S
S
S
+
NC
NC
O
S PPh3, BF4
Me
Me
S
1C
2
ACN, -78°C, N 2, tBuOK
Me
Me
S
S
S
S
S
S
S
Me
S
CN
3 83%
Scheme 7
S
S
S
S
4a: R= CH3
S
4b: R= R= CH2
4c: R=R= (CH2)2
4d: R=R= (CH2)
1)EtOH
2)RX
S
S
Me
Me
S
CN
CN
3
4a-d 52-83%
Scheme 8
All π-extended donors exhibit two fully reversible oxidation waves (E1OX and E2OX).
The half-wave potentials are reported in Table 1. These data demonstrated the remarkably
strong electron donor properties of compounds 3 and 4a–d, which are formed by covalent
attachment of triMeTTF and its 1,3-dithiole derivative. The good reversibility of the first
and second redox steps for 3 and 4a–d demonstrates that the oxidized species are stable.
It is striking that the oxidation potentials of 3 and 4a–d are significantly lower than those
observed for independent TTF and TMTTF, which are at the origin of very numerous
conductive and superconductive salts. This demonstrates the marked possibility to produce
new electric materials with desired properties by use of these precursors. The differences
between the first and the second oxidation potentials (ꢀEOX) in all π-extended TTFs
are higher than that found in the parent unsubstituted TTF taken as reference (318 mV).
These results can be attributed to the increased on-site Coulomb repulsion, which implies
that the delocalization of positive charges over the whole TTF molecule is not as pronounced
in the dication.
Table 1 Oxidation potentials of compounds 3 and 4a–d
Donor
E1ox
E2ox
ꢀ Eox
3
4a
4b
4c
4d
TTF
TMTTF
483
526
525
512
553
654
604
827
874
944
909
970
972
1039
344
348
419
397
417
318
435

NEW π-EXTENDED DONORS
1749
Tentative preparation and characterization of some complexes derived from com-
pounds 3 and 4a–d were undertaken and isolated by a chemical redox reaction between
π-extended donors and TCNQ. In each experiment, equimolar amounts (0.1 mmol.) of the
donor and TCNQ were separately dissolved in boiling acetonitrile and then mixed. The
resultant dark solution was then stored at room temperature for several days. The precipitate
was then separated by filtration and three of these complexes, i.e., (3)2TCNQ, (4a)2TCNQ,
and (4d)2TCNQ obtained as black powders, were analyzed.
The electrical conductivities of the isolated charge transfer complexes were measured
using a two-probe technique on compressed pellets. The results are collected in Table 2.
It is established that the complexes of type TTF-TCNQ must satisfy two conditions
to give a conductor. The first requires the presence of a crystal structure composed of
regular segregated stacks . . . DDD-AAA . . . of donors and acceptors,23 while the second
is a partial electron transfer (0 < ρ < 1) between these two species. Any of mixed stack
“sandwich” structures . . . DAD-DAD . . . of the salt, or the absence of a charge transfer
800
E2
ox
600
E1
400
ox
200
0
-200
-400
-600
-0 ,2
0,0
0,2
0,4
0,6
0,8
1,0
1 ,2
1,4
E (V )
Figure 2 Cyclic voltammogram of compound 3.

1750
A. ZITOUNI ET AL.
Table 2 Characteristics and electrical conductivities of compounds 3 and 4a–d
Donor
Acceptor
Color
Morphology
σ (S·cm−1
)
3
TCNQ
TCNQ
TCNQ
TCNQ
TCNQ
Black
Black
—
—
Brown
Needles
Powder
—
—
Powder
10−6
10−8
—
—
10−9
4a
4b
4c
4d
(molecular complex) or a complete charge transfer (ionic complex) lead to an insulating
material.24,25
Due to the lack of monocrystals, various authors were able to estimate the rate of
charge transfer of this type of complex from different techniques,26 and in particular from
the IR spectra.27,28 Based on the relation between the frequency of vibration of the CN
group and the degree of charge transfer for reference compounds such as TCNQ (νCN
=
2227 cm−1, ρ = 0 e−/molecule), TCNQ−K+ (2183 cm−1, 1), TTF-TCNQ (2204 cm−1
,
0.59), HMTTF-TCNQ (2195 cm−1, 0.72), TMTTF-TCNQ (2200 cm−1, 0.65), TMTSF-
TCNQ (red) (2217 cm−1, 0.23), etc., we were able to draw a ρ = f(νCN) straight line, which
corresponds to the correlation between the vibration frequencies of the CN group and the
degree of charge transfer for different TTFs. We recorded the IR spectra of all complexes
prepared in the 2100 and 2250 cm−1 range, and we obtained the vibration frequency of
the CN group for each complex. The νCN frequency was then used on the calibration ρ =
f(νCN) curve to determine the approximate value of the degree of charge transfer ρ. The
results are reported in Table 3.
It appears that the non-conducting materials 3-TCNQ and 4a,d-TCNQ do not present
a partial degree of charge transfer. These values (ρ = 0.162, 0.175, 0.285) are comparable
to the known insulator TMTSF-TCNQ (red) (ρ = 0.23). Considering these results, it is
reasonable to propose that the non-conducting charge transfer complexes studied here
possess a mixed stack (sandwich) structure, or a large separation between stacked donors,
or the presence of structural disorder,19 etc.
As for the nonconducting 5d-TCNQ, the value of the degree of charge transfer is
about 0.43 e−/molecule. This value is in a range that would favor a metallic behavior for
this salt. Since it is semiconducting, we are led to believe that the requirement regarding
the stacking of the molecules is not met. Several explanations for this behavior might
be a mixed stack (sandwich) structure, a large separation between stacked donors, or the
presence of structural disorder.
The preparation and characterization of mixed valence salts of the new π-extended
donors 4a–d is, therefore, a fascinating prospect.
Table 3 Degree of charge transfer of TCNQ complexes
Complex
νCN (cm−1
)
ρ (e−/mole)
σ (S·cm−1
)
3-TCNQ
4a-TCNQ
4d-TCNQ
2215
2219
2220
0.285
0.175
0.162
10−6
10−8
10−9

NEW π-EXTENDED DONORS
1751
CONCLUSIONS
A new series of π-extended TTFs has been developed by using the Wittig reaction
between a phosphorus ylide and an aldehyde group introduced in a unit TTF. The study
by electrochemical cyclic voltammetry confirms the potential of these new compounds.
From these new donors, organic materials were obtained as powders. The results show
non-conductor behavior for all the synthesized complexes.
EXPERIMENTAL
NMR spectra were recorded as CDCl3 solutions on a Bruker AC 250 spectrometer
operating at 250 MHz. FAB+ mass spectra were recorded on a Trace GC 2000/Finngan.
Melting points were obtained on a Bu¨chi B-540 apparatus. Microanalyses (AE) were
performed at the microanalysis center with an Elementar Vario EL III, C,H,N,S analyzer
(Germany). Cyclic voltammetry measurements were carried out on a potentiostat PGZ 301
Dynamic-EIS Voltammeter.
2-Dimethoxyphosphoryl-4,5-dimethyl-1,3-dithiole (1a)
To a solution of 4 g (14.5 mmol) of dithiolium salt in 60 mL of anhydrous CH3CN,
2.1 mL (17.9 mmol) of freshly distilled P(OMe)3 and 2.6 g (17.9 mmol) of NaI were
successively added. The resulting mixture was kept overnight under nitrogen at room
temperature. After evaporation of the solvent, the residue was taken back into 150 mL of
ether, then washed with water (2 × 50 mL) and dried over MgSO4 before being concentrated
1
under reduced pressure to supply 1a as a red oil (83% yield). H NMR: δ = 1.95 (s, 6H,
CH3), 3.88 (d, 6H, OCH3), 4.73 (d, 1H, J = 5.6 Hz, CH). MS (FAB+): m/z = 240 (M+).
3,6,7-Trimethyl-tetrathiafulvalene (1)
To a solution of phosphonate 1a (15 g, 62.5 mol) in dry THF (250 mL) under nitrogen
atmosphere at −78◦C, 8.4 g (75 mmol) of sublimated t-BuOK were added. After 1 h at
low-temperature, 21.55 g (62.5 mmol) of imminium salt 1b were added to the reaction
mixture. The reaction was stirred for another 1 h at −78◦C, and then warmed up to room
temperature overnight. The reaction mixture was diluted with ether (250 mL) and was
maintained for 1 h. After filtration over Celite, the filtrate was concentrated under reduced
pressure and diluted with toluene (250 mL). Then acetic acid (15 mL) was added, and
the mixture was stirred for 1 h. The organic phase was washed with water (5 × 100 mL).
After drying over MgSO4, the solvent was concentrated, and the residue was purified by
chromatography on a silica gel column. Evaporation of the solvents and crystallization
from acetonitrile afforded pure 1 as orange solid (60% yield). Mp 103–105◦C. 1H NMR:
δ = 1.95 (s, 6H, CH3), 2.06 (s, 3H, CH3), 5.83 (s, 1H, = CH).
3,6,7-Trimethyltetrathiafulvalene-2-carbaldehyde (2)
A sample of 1 g (4 mmol) triMeTTF 1 was stirred in dry THF (60 mL) under a stream
of nitrogen at −78◦C. A solution of freshly prepared lithium diisopropylamide (4.87 mmol)
was added slowly, and the mixture was stirred for 1.30 h. A solution of Ph(Me)NCHO (0.90
mL, 7.38 mmol) was added portionwise, and the mixture was stirred for 1 h at −78◦C.

1752
A. ZITOUNI ET AL.
The temperature of the reaction was raised to room temperature, and the reaction mixture
was kept overnight with stirring. The mixture was poured into acidified water (8 mL, HCl,
2N). The aqueous phase was extracted with dichloromethane (3 × 30 mL). The combined
organic phases were washed with water, dried over MgSO4, and concentrated under vacuum.
The layers were separated, and the organic phase was dried, filtered, and evaporated. The
reaction product was purified by chromatography (silica toluene:hexane, 1:1, and toluene)
to afford 2 as a dark red powder with 44% yield. Mp 217–218◦C. 1H NMR: δ = 1.93 (s,
6H, CH3), 2.04 (s, 1H, CH3), 9.46 (s, 1H, CHO). MS (FAB+): m/z = 275 (M++1).
2-[4.5-Bis(2-cyanoethyl)-1.3-dithiol-2-ylidene]methyl-3,6,7-
trimethyltetrathiafulvalene (3)
The phosphonium salt 1c18 (0.35 g, 0.56 mmol) was dissolved in dry MeCN (50 mL)
under nitrogen at −78◦C. A solution of 60 mg (0.56 mmol) of t-BuOK was added at this
temperature and the mixture was stirred for 30 min. A solution of the aldehyde 2 (100 mg,
0.25 mmol) in dry THF (10 mL) was used, and the mixture was raised at room temperature
overnight. The THF was removed under vacuum, and the residue was chromatographed on
silica gel (CH2Cl2/hexane, 2:1) to yield 83% 3 as orange powder. Mp 161◦C. 1H NMR: δ =
1.25 (s, 6H, 2CH3), 1.95 (s, 3H, CH3), 2.75 (t, 4H, CH2-CN, J = 5 Hz), 3.12 (t, 4H, SCH2,
J = 6 Hz), 7.25 (s, 1H). MS (FAB+): m/z = 530 (M+). Anal. Calcd. for C19H18N2S8: C,
43.02; N, 5.28. Found: C, 43.51; N, 5.78.
2-[4.5-Bis(methylthio)-1.3-dithiol-2-ylidene]methyl-3,6,7-
trimethyltetrathiafulvalene (4a)
A solution of NaOH (21 mg, 18 mmol) in 4 mL of anhydrous ethanol was added
dropwise to a degassed solution of the TTF 3 (100 mg, 0.18 mmol) in 10 mL of anhydrous
ethanol under nitrogen. The mixture was stirred for 4 h at room temperature, and methyl
iodide (3 equiv.) was added to the mixture. After stirring overnight, the resulting product
was dissolved in CH2Cl2. The organic phases were washed several times with water, dried
over MgSO4, and concentrated. Purification of the product was performed by silica gel
column chromatography (CH2Cl2/hexane, 2:1) and yielded 4a as a black brown powder
(65%). Mp 139◦C. 1H NMR: δ = 1.30 (s, 6H, 2CH3), 2.10 (s, 3H, CH3), 2.80 (s, 3H, SCH3),
3.10 (s, 3H, SCH3), 7.25 (s, 1H). MS (FAB+): m/z = 452 (M+).
2-(4.5-Methylenedithio-1.3-dithiol-2-ylidene)methyl-3,6,7-
trimethyltetrathiafulvalene (4b)
This reaction used the same method as for the synthesis of compound 4a, only adding
3.4 equivalents of dibromomethane (0.44 g) to the TTF 3 (0.2 g, 0.36 mmol) in 20 mL
of ethanol. The crude product was chromatographed on silica gel (CH2Cl2) to give 4b as
brown powder (52%). Mp 119.5◦C. 1H NMR: δ = 1.25 (s, 6H, 2CH3), 2.00 (s, 3H, CH3),
3.6 (s, 2H, CH2S), 7.25 (s, 1H). MS (FAB+): m/z = 436 (M+).

NEW π-EXTENDED DONORS
1753
2-(4.5-Ethylenedithio-1.3-dithiol-2-ylidene)methyl-3,6,7-
trimethyltetrathiafulvalene (4c)
This was obtained similarly from (0.1g, 0.18 mmol) of 3 and three equivalents (48.7
mg) of 1,2-dibromoethane. The compound 4c was obtained as brown powder with 68%
yield. Mp 138.5◦C. 1H NMR: δ = 1.25 (s, 6H, 2CH3). Anal. Calcd. for C15H14S8: C, 40.45;
H, 3.11. Found: C, 41.67; H, 3.83.
2-(4.5-Trimethylenedithio-1.3-dithiol-2-ylidene)methyl-3,6,7-
trimethyltetrathiafulvalene (4d)
This was synthesized in a similar manner from (0.425g, 3.5 equiv.) of 1,3-
dibromopropane and 0.2g (0.36 mmol) of TTF 3 in 20 mL of ethanol as clear brown
1
powder in 74% yield. Mp 133◦C. H NMR: δ = 1.25 (s, 6H, 2CH3), 1.95 (s, 3H, CH3),
2.75 (m, 4H, CH2-CH2), 3.60 (t, 2H, SCH2 J = 7Hz), 7.25 (s, 1H). MS (FAB+): m/z =
464 (M+) Anal. Calcd. for C16H16S8: C, 40.39; H, 3.44. Found: C, 40.03; H, 3.83.
Charge Transfer Complexes (CTC)
The charge transfer complexes were isolated by a chemical redox reaction between
a donor (3 and 4a–d) and TCNQ as the electron acceptor, in equimolar amounts dissolved
in hot MeCN.
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