Synthesis of a disulfide functionalized diacetylenic derivative of carbazole as building-block of polymerizable self-assembled monolayers

Article abstract of DOI:10.2478/s11696-013-0437-2

A new symmetrical disulfide containing a diacetylenic unit and bearing a fluorescent carbazolyl end-group forming polymerizable self-assembled monolayers on metallic nanostructures has been synthesized. Suitable modifications of the synthetic steps involved in the synthesis of such derivatives were made in order to assure better synthetic pathway. Conversion of the tosylated derivative into the final symmetrical disulfide is carried out using sodium hydrosulfide (NaSH).

Full text of DOI:10.2478/s11696-013-0437-2

Chemical Papers
DOI: 10.2478/s11696-013-0437-2
ORIGINAL PAPER
Synthesis of a disulfide functionalized diacetylenic derivative
of carbazole as building-block
of polymerizable self-assembled monolayers
b
a,bSushilkumar A. Jadhav*, Massimo Maccagno
aDepartment of Applied Science and Technology, Polytechnic University of Turin, 10129 Turin, Italy
bDepartment of Chemistry and Industrial Chemistry, University of Genoa, 16146 Genoa, Italy
Received 21 March 2013; Revised 6 May 2013; Accepted 10 May 2013
A new symmetrical disulfide containing a diacetylenic unit and bearing a fluorescent carbazolyl
end-group forming polymerizable self-assembled monolayers on metallic nanostructures has been
synthesized. Suitable modifications of the synthetic steps involved in the synthesis of such derivatives
were made in order to assure better synthetic pathway. Conversion of the tosylated derivative into
the final symmetrical disulfide is carried out using sodium hydrosulfide (NaSH).
c
ꢀ 2013 Institute of Chemistry, Slovak Academy of Sciences
Keywords: symmetrical disulfide, diacetylene, sodium hydrosulfide
Introduction
gated polydiacetylene chains but they also strengthen
the scaffold of the organosulfur compounds around
nanostructures such as the nanoparticles. Polymeriz-
able monolayers of polydiacetylenes have shown their
potential applications in molecular electronics (Okawa
et al., 2011, 2012). Conducting properties and higher-
performance are the main features of polydiacetlenes
fabricated in monolayers on different substrates such
as semiconducting materials which may prove to be al-
ternatives to conventional silicon-based devices (Man-
dal et al., 2011). The photo-polymerization scheme in
monolayers of these compounds is shown in Fig. 1.
Synthesis and physical and optical characteriza-
tion of a particular class of polydiacetylenes have been
previously reported (Alloisio et al., 2007), namely
the poly(carbazolyldiacetylenes) (PCDAs) of the gen-
Organosulfur compounds, because of their capa-
bility to get chemisorbed on metallic surfaces, espe-
cially on gold ones, are well-known building-blocks
for the construction of self-assembled monolayers
(SAMs) (Ulman, 1991; Jadhav, 2012a, 2012b; Miyano
& Maeda, 1986; Wenzel & Atkinson, 1989; Mino et al.,
1991, 1992; Charyach et al., 1993; Batchelder et al.,
1994; Kim et al., 1995). The surface modification by
SAMs allows tailoring the interfacial properties of the
nanostructures both in two (chip) and three (nanopar-
ticles) dimensional surfaces. Both thiols and disulfides
are frequently utilized building-blocks for the con-
struction of monolayers or for the surface modification
of gold surfaces; hence, synthesis of these compounds
and their derivatives has drawn increased attention in
recent years (Joly et al., 2010; Operamolla et al., 2007;
Kota et al., 2012; Jadhav, 2012b; Zhao et al., 2012).
Incorporation of polymerizable diacetylene groups in
such compounds provides them with the possibility
of being polymerized forming polymers with highly
conjugated backbones (polydiacetylenes). The result-
ing assemblies not only possess the conducting conju-
—
—
eral formula: R—(CH2)m—C—C—C—C—(CH2)n—
—
—
—
—
S—S—(CH2)n—C—C—C—C—(CH2)m—R, where
—
—
R is the electron–donor end-group. We have also
recently reported the synthesis of thiols and their
symmetrical disulfides containing fluorescent end-
groups, such as the carbazole and benzotriazole groups
as building-blocks of monolayer formations (Jadhav,
2012b). The presence of fluorescent groups makes
*Corresponding author, e-mail: sushilkumar.jadhav@polito.it

ii
S. A. Jadhav, M. Maccagno/Chemical Papers
Fig. 1. Photo-polymerization in monolayer of diacetylene functionalized disulfide.
these compounds attractive building-blocks because of
their enhanced hole-transporting, photo-conducting,
and nonlinear optical properties. The self-assembled
monolayers of functionalized diacetylene disulfides
containing fluorescent groups on gold have shown the
formation of robust polymeric chains with foresee-
able appealing optoelectronic behavior. The construc-
tion of self-assemblies on noble-metal surfaces followed
by polymerization with UV light of such class of di-
acetylenes has been reported (Giorgetti et al., 2006;
Cavalleri et al., 2005; Alloisio et al., 2004). Follow-
ing the results obtained for similar derivatives, the
present study is based on the synthesis of new deriva-
tives, purposely designed in order to improve the per-
formance in their construction of SAMs by means
of structural or electronic modifications of the orig-
inal array. In the synthesis reported here, distan-
tiation of the carbazole end-group from the poly-
merization site (i.e., the diacetylenic unit present in
the same molecule) was attempted to simplify the
synthetic protocol of the synthesis of such deriva-
tives. Researchers attempted to study the effect of a
methylene spacer located both before and after the
diacetylenic unit, on the extent of the conjugation
and properties of the resulting polydiacetylenes (Men-
zel et al., 2000). The new member of our synthetic
series will help us to understand this phenomenon
as well as the effect of the carbazole group on the
conducting properties of the resulting polydiacety-
lene containing monolayers. In this paper, the syn-
thesis of a new member of the disulfide series called
CPDS9 (VIII ) (where R = 9-H carbazole, m = 3,
n = 9; refer to the general formula above) is re-
ported.
(Italy) and were used as received. Petroleum ether
and light petroleum ether refer to the fractions boil-
ing in the range of 40–60◦C and 80–110◦C, respec-
tively. Solvents used for all the reactions and as eluents
for chromatographic separations were distilled prior to
use. Anhydrous solvents were syringed under argon.
Pyridine was distilled twice prior to use, first from
KOH pellets and then from CaH2. The commercial
reagents mentioned in the synthetic procedures were
extra pure. The synthetic protocol followed is shown
in Fig. 2.
1H NMR (300 MHz) and 13C NMR (75 MHz) spec-
tra (Table 1) were taken on a Varian Gemini 300
spectrometer (Varian, USA); TMS was used as the
internal standard. All deuterated solvents mentioned
were of spectroscopic grade and they were purchased
from Sigma–Aldrich. Chemical shifts are given in δ,
coupling constant (J) in Hz. Electronic absorption
and emission spectra were recorded at room tempera-
ture on a Perkin–Elmer Lambda 9 spectrophotometer
(Perkin–Elmer, USA).
9-(Pent-4-yn-1-yl)-9H-carbazole (II)
9H-Carbazole (I; 10.3 g, 616 mmol) was dis-
solved in warm toluene (400 mL). The solution was
left to cool slowly until the saturation temperature
was reached and then 5-chloro-1-pentyne (9.47 g,
924 mmol), tetrabutylammonium bromide (0.99 g,
31 mmol), and 50 % aq. solution of NaOH (63.7 mL)
were added. The reaction mixture was then heated at
80◦C until the completion of the reaction (approxi-
mately 24 h). The mixture was then acidified to pH
1 by adding concentrated HCl (37 %), diluted with
water, and extracted with diethyl ether. The organic
layer was washed to neutrality with water and then
dried over Na2SO4. Evaporation of the solvent gave
a yellowish white solid which was recrystallized from
boiling ethanol yielding 14.0 g (96 %), m.p. 61.1–
61.5◦C.
Experimental
General
All chemicals were purchased from Sigma–Aldrich

S. A. Jadhav, M. Maccagno/Chemical Papers
iii
Fig. 2. Synthetic protocol for CPDS9: i – 5-chloro-1-pentyne, NaOH, Bu4NI, water/toluene, 80◦C, 24 h, 96 %; ii –BuLi, I2, THF,
0◦C, 5 h, 99 %; iii – CuCl, NH3/NH2OH · HCl/EtOH, r.t., 90 min, 90 %; iv – pyridine, 40◦C → r.t., 20 h, 57 %; v –
p-tosylchloride, pyridine, 10 ◦C → r.t., 40 h, 75 %; vi – NaSH, EtOH, 40–45◦C, 12 h, 41 %.
9-(3-Iodopent-4-yn-1-yl)-9H-carbazole (III)
ing dark-red solution was allowed to react for 5 h
still at 0◦C. The excess of iodine was destroyed with
a 5 mass % aq. solution of sodium sulfite, and the
resulting colorless solution was diluted with water
and then repeatedly extracted with diethyl ether.
After drying with anhydrous sodium sulfate, evap-
oration of the organic solvent under reduced pres-
sure gave a dark-brown residue which was recrystal-
lized from ethanol yielding 20.0 g (99 %), m.p. 75.4–
75.6◦C.
II (13.0 g, 56 mmol) was introduced into a two-
necked flask equipped with a thermometer and a
dropping funnel, and the system was put under ar-
gon. THF (400 mL) was added, and the resulting
clear solution was cooled to 0◦C and kept under
magnetic stirring while adding a 1.5 M solution of
butyllithium in hexane (64 mmol). After 40 min, io-
dine (21.0 g, 84 mmol) was added, and the result-

iv
S. A. Jadhav, M. Maccagno/Chemical Papers
Table 1. Spectral data of newly prepared compounds
Compound
Spectral data
II
1H NMR (CDCl3), δ: 2.12 (quin, 2H, J = 6.6 Hz), 2.15 (s ,1H), 2.24 (t, 2H, J = 6.6 Hz), 4.47 (t, 2H, J = 6.6 Hz),
7.22–7.28 (m, 2H), 7.45–7.49 (m, 4H), 8.11 (d, 2H, J = 7.8 Hz)
13C NMR (CDCl3), δ: 16.5, 28.0, 41.7, 69.8, 83.7, 108.9, 119.2, 120.6, 123.2, 126.0, 140.7
MS, m/z: 233 (M+
)
III
VI
1H NMR (CDCl3), δ: 2.10 (quin, 2H, J = 6.9 Hz), 2.39 (t, 2H, J = 6.9 Hz), 4.45 (t, 2H, J = 6.9 Hz), 7.22–7.24 (m,
2H), 7.45–7.48 (m, 4H), 8.17 (dd, 2H, J = 7.8 Hz)
13C NMR (CDCl3), δ: 18.8, 28.0, 41.7, 93.8, 108.9, 119.3, 120.7, 123.2, 126.0 140.6
MS, m/z : 359 (M+
)
1H NMR (CDCl3), δ: 1.26–1.59 (m, 14H), 2.11 (quin, 2H, J = 6.6 Hz), 2.15 (s, 1H), 2.29 (t, 4H, J = 6.6 Hz), 3.63
(t, 2H, J = 6.6 Hz), 4.45 (t, 2H, J = 6.6 Hz), 7.23–7.26 (m, 2H), 7.46–7.48 (m, 4H), 8.01 (d, 2H, J = 7.5 Hz)
13C NMR (CDCl3), δ: 17.3, 19.5, 25.9, 27.9, 28.5, 29.1, 29.3, 29.6, 29.7, 33.0, 41.8, 63.3, 65.3, 66.8, 76.2, 78.5, 108.9,
119.2, 120.6, 123.1, 126.0, 140.6
MS, m/z : 399 (M+
)
VII
1H NMR (CDCl3), δ: 1.25–1.41 (m, 14H), 1.49–1.67 (m, 4H), 2.29 (t, 2H, J = 6.75 Hz), 2.44 (s, 3H), 4.01 (t, 2H, J
= 6.5 Hz), 4.45 (t, 2H, J = 6.5 Hz), 7.21–7.26 (m, 2H), 7.34 (d, 2H, J = 8.7 Hz), 7.46–7.48 (m, 4H), 7.79 (d, 2H, J
= 8.4 Hz), 8.1 (d, 2H, J = 7.8 Hz)
13C NMR (CDCl3), δ: 17.3, 19.5, 21.9, 25.5, 27.9, 28.5, 29.0, 29.0, 29.1, 29.2, 29.5, 41.8, 65.4, 66.8, 70.9, 76.2, 78.4,
108.9, 119.2, 120.6, 123.1, 126.0, 128.1, 130.0, 133.5, 140.6, 144.9
VIII
1H NMR (CDCl3), δ: 1.31–1.54 (m, 10H), 1.52–1.72 (m, 4H), 2.11 (quin, 2H, J = 6.6 Hz), 2.29 (t, 4H, J = 6.8 Hz),
2.68 (t, 2H, J = 7.5 Hz), 4.44 (t, 2H, J = 6.6 Hz), 7.21–7.26 (m, 2H), 7.46–7.48 (m, 4H), 8.10 (d, 2H, J = 7.8 Hz)
13C NMR (CDCl3), δ: 17.3, 19.5, 28.0, 28.5, 28.7, 29.1, 29.3, 29.4, 29.4, 29.6, 39.4, 41.8, 65.4, 66.8, 76.2, 78.5, 108.9,
119.2, 120.6, 123.1, 126.0, 140.6
Cu(I) salt of 10-undecyn-1-ol (V)
raphy (dichloromethane/diethyl ether, ϕr = 10 : 1).
The separation gave a yellowish thick oil VI (5.5 g,
57 %).
A solution of 10-undecyn-1-ol (IV; 16.5 mL,
85.9 mmol) in ethanol (200 mL) was slowly added to a
solution of freshly prepared CuCl (85.0 g, 859 mmol)
in 12 N ammonia (3.5 L) containing some hydroxyl-
amine hydrochloride under efficient stirring. After
completion of the addition, stirring was continued
for 90 min while small aliquots of hydroxylamine hy-
drochloride were added portion-wise; the yellow pre-
cipitate formed was then filtered and washed in se-
quence with water, ethanol, and diethyl ether yielding
V (17.9 g, 90 %), as a yellow powder.
14-(9H-9-Carbazolyl)hexadeca-12,14-di-yn-1-
yl p-toluenesulfonate (VII)
Dry pyridine (3.7 mL) was added to a mag-
netically stirred solution of VI (4.3 g, 11.6 mmol)
in dry dichloromethane (172 mL) which was then
cooled to 10◦C and added with p-tosylchloride (3.6 g,
17.3 mmol) in small portions. After standing for ad-
ditional 10 min at the same temperature, the mixture
was allowed to reach room temperature, left under
stirring for 40 h, poured into a mixture of concentrated
HCl (42 mL) and crushed ice, and finally extracted
with ethyl ether. The organic layer was washed repeat-
edly with water, dried over anhydrous sodium sulfate,
and the solvent was removed under reduced pressure
to give a residue which was flash-chromatographed on
a silica gel column (dichloromethane/petroleum ether,
ϕr = 1 : 3). Crude product from the chromatographic
separation gave a thick orange oil VII (8.0 g, 75 %).
14-(9H-9-Carbazolyl)hexadeca-12,14-diyn-1-ol
(VI)
A slurry of V (14.6 g, 63.3 mmol) in dry pyridine
(227 mL) was warmed to 40◦C under argon. A solution
of III (19.1 g, 57.7 mmol) in dry pyridine (142 mL) was
added to the resulting yellow suspension over a period
of 40 min. After 20 h at room temperature, the mix-
ture was cooled by an addition of crushed ice, poured
into an excess (1.2 L) of concentrated HCl, diluted
with water, and the aq. solution was extracted with
diethyl ether. After the separation, the organic layer
was washed with 5 vol. % HCl, water, and dried over
anhydrous sodium sulfate. Evaporation of the solvent
gave a residue which was purified by flash chromatog-
16-(9H-9-Carbazolyl)hexadeca-10,12-diyn-1-yl
disulfide (VIII, CPDS9)
The tosylated diacetylene, VII (1.55 g, 8 mmol),
was dissolved in a minimum amount of absolute

S. A. Jadhav, M. Maccagno/Chemical Papers
v
Fig. 3. Alternative routes for the conversion of an alcohol into a disulfide, where R can be an alkyl or aryl group: i – p-tosylchloride,
pyridine; ii – NaI, acetone; iii – CH3COSK, DMF; iv – KOH/acetone; v – NaSH, EtOH.
ethanol. Sodium hydrogen sulfide (0.925 g, 16.08
mmol) was added and the mixture was sonicated at
40–45◦C for 12 h. The solution was then diluted with
chloroform and washed with 1 N HCl. After drying
over sodium sulfate, the organic phase was evaporated
yielding a thick yellow liquid which was purified by
flash chromatography (petroleum ether/ethyl acetate,
ϕr = 1 : 2) ratio. The chromatographic separation pro-
vided a thick oil VIII (463 mg, 41 %).
moiety by varying the number of the methylenic units,
in order to evaluate any possible change in the prop-
erties caused by an odd number (m = 3) of the methy-
lene units between carbazole and diacetylene and an
odd number of methylene units (n = 9) between di-
acetylene and the anchoring group disulfide.
The synthesis of CPDS-9 disulfide was performed
starting from 9H-carbazole by means of the protocol
shown in Fig. 2. The synthetic procedure involved the
condensation of 5-chloro-1-pentyne with 9H-carbazole
in strongly basic conditions to give compound II, fol-
lowed by the iodination of the terminal acetylenic hy-
drogen with iodine, then the condensation of the iod-
inated intermediate (III ) with the copper salt of 10-
undecyn-1-ol (V ) providing alcohol VI, its tosylation
and the conversion of the tosylated intermediate (VII )
into the final disulfide VIII with the help of sodium
hydrogen sulfide in a single step which involves the
nucleophilic displacement of the tosylate group by the
thiol group. The final disulfide VIII was obtained in
41 % of final yield.
There are two possible main routes for the conver-
sion of the alcohol to the corresponding disulfide as
shown in Fig. 3. As it can be seen, the first route (i
+ ii + iii + iv) involves two more steps (Alloisio et
al., 2007) than the second one (i + v). Both routes
lead to the same disulfide in similar overall yields: the
second route, which involves less synthetic steps and
less reagents, has obviously been chosen for the syn-
thesis that is reported here. This was carried out us-
ing sodium hydrosulfide, which can convert the alcohol
into disulfide directly (Jadhav, 2012b), as the reagent.
The reaction time for the conversion of the tosylated
alcohol into the desired symmetrical disulfide depends
on the type of alcohol involved. Nucleophilic displace-
ment of the tosylate group first leads to the formation
of a thiol, which is then oxidized to the final disulfide.
The long reaction time (12 h) ensures the conversion
of all thiols formed initially into disulfides.
Results and discussion
Considering the experience obtained in previ-
ous studies on synthesized derivatives (Alloisio et
al., 2007; Jadhav, 2012b), the synthesis of homolo-
gous carbazolyldiacetylene derivative R—(CH2)m—
—
—
—
—
C—C—C—C—(CH2)n—S—S—(CH2)n—C—C—
—
—
—
C—C—(CH2)m—R characterized by a different num-
—
ber of metylene units between the diacetylenic moiety
and the carbazole end-group R was done (Fig. 2). Tao
and Bernasek (2007) reported studies on the effect of
odd or even number of units in a molecule and on
the properties of the monolayers formed from various
odd/even numbered units. The structural unit caus-
ing a change in the self-assembly monolayer properties
can be one methylene (CH2) group, one metal atom,
or a more complicated unit. According to them, in
diacetylenes, the number of methylene units located
before and after the polymerizable group, significantly
affects the properties of the resulting polydiacetylenes.
When studying these self-assembled thin films, a great
number of new odd/even chain-length effects has been
observed. They originate from various complex inter-
actions between the self-assembled molecules and the
substrate on which they are constructed, interactions
between the packed molecules in the monolayer, or
both. More importantly, these structural odd/even ef-
fects induce various alterations of chemical, physical,
and surface, and interfacial properties such as chem-
ical reactivity, electronic or electrochemical proper-
ties, friction behavior (Tao & Bernasek, 2007). The
present approach to the synthesis of CPDS9 was aimed
at spacing the carbazolyl group from the diacetylenic
UV-VIS and fluorescence spectra
The UV-VIS absorption spectra of CPDS9 were

vi
S. A. Jadhav, M. Maccagno/Chemical Papers
synthesized derivative involved carbazole as a flores-
cent nucleus and a polymerizable diacetylene moiety
which can undergo photochemical and thermal poly-
merization to give a polydiacetylene. The steps in-
volved in the synthesis of the molecule can be applied
in the synthesis of similar derivatives of varying chain
lengths (number of methylene spacers) to space ei-
ther the carbazole group or the disulfide group from
the polymerizable diacetylene moiety present in the
molecule or of similar derivatives containing different
fluorescent groups.
Acknowledgements. The authors would like to thank the
University of Genoa, Italy for the research funding and Prof.
Sergio Thea and Prof. Giovanni Petrillo from the Department
of Chemistry and Industrial Chemistry, University of Genoa,
Italy, for their guidance.
Fig. 4. UV-VIS spectrum of CPDS9 in toluene (dashed line)
and chloroform (solid line).
References
Alloisio, M., Sottini, S., Riello, P., Giorgetti, E., Margheri,
G., Cuniberti, C., & Dellepiane, G. (2004). AFM, SEM
and GIXRD studies of thin films of red polycarbazolyld-
lacetylenes. Surface Science, 554, 68–75. DOI: 10.1016/j.
susc.2004.02.011.
Alloisio, M., Demartini, A., Cuniberti, C., Petrillo, G., Thea,
S., Giorgetti, E., Giusti, A., & Dellepiane, G. (2007). Self-
assembled monolayers of disulfide-functionalized diacetylenes
on gold films and nanoparticles. Journal of Physical Chem-
istry C, 111, 345–353. DOI: 10.1021/jp0640777.
Batchelder, D. N., Evans, S. D., Freeman, T. L., Haeussling, L.,
Ringsdorf, H., & Wolf, H. (1994). Self-assembled monolayers
containing polydiacetylenes. Journal of the American Chem-
ical Society, 116, 1050–1053. DOI: 10.1021/ja00082a028.
Cavalleri, O., Prato, M., Chincarini, A., Rolandi, R., Canepa,
M., Gliozzi, A., Alloisio, M., Lavagnino, L., Cuniberti, C.,
Dell’Erba, C., & Dellepiane, G. (2005). Self-assembled mono-
layers of a novel diacetylene on gold. Applied Surface Science,
246, 403–408. DOI: 10.1016/j.apsusc.2004.11.045.
Charyach, D. H., Nagy, J. O., Spevak, W., & Bedvarski, M.
D. (1993). Direct colorimetric detection of a receptor-ligand
interaction by a polymerized bilayer assembly. Science, 261,
585–588. DOI: 10.1126/science.8342021.
Giorgetti, E., Muniz-Miranda, M., Margheri, G., Giusti, A., Sot-
tini, S., Alloisio, M., Cuniberti, C., & Dellepiane, G. (2006).
UV polymerization of self-assembled monolayers of a novel
diacetylene on silver: A spectroscopic analysis by surface
plasmon resonance and surface enhanced Raman scattering.
Langmuir, 22, 1129–1134. DOI: 10.1021/la0514157.
Jadhav, S. A. (2012a). Functional self-assembled monolay-
ers (SAMs) of organic compounds on gold nanoparti-
cles. Journal of Materials Chemistry, 22, 5894–5899. DOI:
10.1039/c2jm14239b.
Fig. 5. Normalized absorption (solid line) and fluorescence
(dashed line) spectrum of CPDS9 in toluene.
measured in two different solvents. Both in toluene
and in chloroform, the UV-VIS spectrum of CPDS9
showed two characteristic absorption bands of the car-
bazole heteroring with the maxima at 330 nm and
344 nm attributed to the absorption by two chro-
—
—
mophores C C and C N, respectively (Fig. 4). In
—
—
the fluorescence spectrum of CPDS9 (Fig. 5) exci-
tation and absorption spectra with a Stokes shift of
6.5 nm with respect to the absorption and emission
maxima are shown.
Conclusions
Jadhav, S. A. (2012b). Synthesis of fluorescent long-chain thi-
ols/disulfides as building-blocks for self-assembled monolay-
ers preparation. Central European Journal of Chemistry, 10,
295–299. DOI: 10.2478/s11532-011-0140-5.
Joly, K. M., Mirri, G., Willener, Y., Horswell, S. L., Moody, C.
J., & Tucker, J. H. R. (2010). Synthesis of an achiral isomer
of lipoic acid as an anchor group for SAM formation on gold
surfaces. Journal of Organic Chemistry, 75, 2395–2398. DOI:
10.1021/jo9024545.
Simplified methods for the synthesis of targeted
building-blocks (ligands) for their surface self-assembly
on metallic nanostructures are welcomed by the ma-
terial scientists. In the present study, a synthesis of
diacetylene functionalized disulfide monomer was car-
ried out applying simplified synthetic procedures with
lower time and reagents demand. The use of sodium
hydrosulfide as the reagent decreased the number of
the steps involved in the conversion of the alcohol in-
termediate into the final symmetrical disulfide. The
Kim, T., Crooks, R. M., Tsen, M., & Sun, L. (1995). Poly-
meric self-assembled monolayers. 2. Synthesis and character-
ization of self-assembled polydiacetylene mono- and multilay-

S. A. Jadhav, M. Maccagno/Chemical Papers
vii
ers. Journal of the American Chemical Society, 117, 3963–
3967. DOI: 10.1021/ja00119a010.
Kota, R., Samudrala, R., & Mattern, D. L. (2012). Synthesis
of donor-σ-perylenebisimide-acceptor molecules having PEG
swallowtails and sulfur anchors. Journal of Organic Chem-
istry, 77, 9641–9651. DOI: 10.1021/jo301701a.
Mandal, S. K., Okawa, Y., Hasegawa, T., & Aono, M. (2011).
Rate-determining factors in the chain polymerization of
molecules initiated by local single-molecule excitation, ACS
Nano, 5, 2779–2786. DOI: 10.1021/nn103231j.
Menzel, H., Horstmann, S., Mowery, M. D., Cai, M., & Evans,
C. E. (2000). Diacetylene polymerization in self-assembled
monolayers: Influence of the odd/even nature of the methy-
lene spacer. Polymer, 41, 8113–8119. DOI: 10.1016/s0032-
3861(00)00148-8.
Mino, N., Tamura, H., & Ogawa, K. (1991). Analysis of color
transitions and changes on Langmuir-Blodgett films of a
polydiacetylene derivative. Langmuir, 7, 2326–2341. DOI:
10.1021/la00058a060.
Mino, N., Tamura, H., & Ogawa, K. (1992). Photoreactivity
of 10,12-pentacosadiynoic acid monolayers and color transi-
tions of the polymerized monolayers on an aqueous subphase.
Langmuir, 8, 594–598. DOI: 10.1021/la00038a047.
Miyano, K., & Maeda, T. (1986). Photoluminescence, ab-
sorption, and Raman spectra of a polydiacetylene mono-
layer. Physical Review B, 33, 4386–4388. DOI: 10.1103/phys-
revb.33.4386.
Okawa, Y., Mandal, S. K., Hu, C. P., Tateyama, Y., Goedecker,
S., Tsukamoto, S., Hasegawa, T., Gimzewski, J. K., & Aono,
M. (2011). Chemical wiring and soldering toward all-molecule
electronic circuitry. Journal of the American Chemical So-
ciety, 133, 8227–8233. DOI: 10.1021/ja111673x.
Okawa, Y., Akai-Kasaya, M., Kuwahara, Y., Mandal, S. K., &
Aono, M. (2012). Controlled chain polymerisation and chem-
ical soldering for single-molecule electronics. Nanoscale, 4,
3013–3028. DOI: 10.1039/c2nr30245d.
Operamolla, A., Omar, O. H., Babudri, F., Farinola, G. M.,
& Naso, F. (2007). Synthesis of S-acetyl oligoarylenedithi-
ols via Suzuki–Miyaura cross-coupling. Journal of Organic
Chemistry, 72, 10272–10275. DOI: 10.1021/jo701918z.
Tao, F., & Bernasek, S. L. (2007). Understanding odd-even
effects in organic self-assembled monolayers. Chemical Re-
views, 107, 1408–1453. DOI: 10.1021/cr050258d.
Ulman, A. (1991). An introduction to ultrathin organic films.
New York, NY, USA: Academic Press.
Wenzel, M., & Atkinson, G. H. (1989). Chromatic properties
of polydiacetylene films. Journal of the American Chemical
Society, 111, 6123–6127. DOI: 10.1021/ja00198a020.
Zhao, C., Li, L. Y., Guo, M. M., & Zheng, J. (2012). Func-
tional polymer thin films designed for antifouling materi-
als and biosensors. Chemical Papers, 66, 323–339. DOI:
10.2478/s11696-012-0147-1.