Synthesis of two complementary molecular moulds

Article abstract of DOI:10.1002/ejoc.200800954

The synthesis of two complementary molecular moulds is described. These molecules comprise a polyaromatic central part and four lateral bulky tert-butylphenyl or di-tertbutylphenyl groups so that when they are deposited onto a surface, a cavity prone to metallic moulding is created.

Full text of DOI:10.1002/ejoc.200800954

FULL PAPER
DOI: 10.1002/ejoc.200800954
Synthesis of Two Complementary Molecular Moulds
Régis Barattin[a] and André Gourdon*[a]
Keywords: Arenes / Molecular devices / Molecular electronics / Self-assembly
The synthesis of two complementary molecular moulds is de-
scribed. These molecules comprise a polyaromatic central
part and four lateral bulky tert-butylphenyl or di-tert-
butylphenyl groups so that when they are deposited onto a
surface, a cavity prone to metallic moulding is created.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
to fabricate metallic circuitries, in a bottom-up approach,
by diffusion and molecular trapping of metallic atoms. Fig-
ure 1 illustrates such a concept.
Introduction
One of the big challenges for molecular electronics is to
find a way to build integrated circuits through a bottom-
up approach from the molecular scale. Along this line, we
recently showed that suitable molecules can not only re-
structure[1] to create holes or trenches in a metallic surface[2]
but also be used as molecular moulds to fabricate metallic
nanowires[3] or clusters[4] on a surface. These moulds com-
prise a polyaromatic central part, which favours the interac-
tion with metallic atoms, and spacers that lift the polyaro-
matic board above the surface; this creates a cavity under the
plane in which metallic atoms can be trapped. This family
of molecules has been named “molecular landers”.[5] We
have performed this moulding with two different experi-
mental setups: (a) Static moulding: the molecular lander is
left to diffuse on a copper surface at room temperature and
self-assembles by adsorption at surface step edges; mobile
metal atoms then gather under the polyaromatic plateau to
form a nanowire extending away from the step edge.[3] We
also confirmed that the shape of the metallic nanowire is a
function of the shape of the molecular mould.[6] (b) Dy-
namic moulding: in this case, the experiment is done at low
temperature[4] so that isolated atoms do not diffuse. The
mould, pushed on the surface by using an STM tip, collects
and transports these metallic atoms (up to six in the de-
scribed experiment), which are trapped in the cavity under
the mould.
Figure 1. Schematic illustration of the formation of metallic lines
on a surface by self-assembly of complementary molecular moulds
and diffusion of metal atoms in the line of cavities.
Results and Discussion
In Figure 1A, two complementary molecular moulds
have been transferred onto a surface and then diffused and
self-assembled; this creates a stable line of cavities in which
(step B) metallic atoms can be trapped. Of course the type
of metallic circuitry, here a linear chain, is a function of the
chemical design and can be varied at will.
For synthetic reasons, we designed two types of moulds
to be coadsorbed onto a surface. It was foreseen that a
lander comprising both two complementary functions
would be fully insoluble, which would have hindered purifi-
cation and characterization steps and prevented sublima-
tion to the substrate.
Figure 2 shows the final design of the molecules. The
central hydrocarbon cores are similar to those used for dy-
namic (compound 1) and static (compound 2) moulding in
ref.[4] and ref.,[3] respectively. These central parts are
equipped with complementary functions, that is, diaminotr-
iazine and imide groups, respectively. Indeed, we recently
showed[8] that the triple hydrogen bonds between these
Our next goal is now to fully use the well-know potential
of molecular self-assembly[7] to organize, on a surface, or-
dered networks of such molecular moulds with the objective
[a] NanoSciences Group, CEMES-CNRS, UP8011,
B. P. 94347, 29 rue J. Marvig, 31055 Toulouse Cedex 4, France
Fax: +33-5-62257999
E-mail: gourdon@cemes.fr
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
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Synthesis of Two Complementary Molecular Moulds
Figure 2. Self-assembly of landers 1 and 2.
groups provided very stable lines of alternant molecules.
Such a good thermal stability is required for room-tempera-
ture diffusion of metallic atoms.
The synthesis of substituted hexaphenylbenzene 1 is out-
lined in Scheme 1. Double Knoevenagel condensation be-
tween 1,2-bis(4-tert-butylphenyl)ethane-1,2-dione[9] and
1,3-bis(4-bromophenyl)acetone[10] gave cyclopentadienone
3 in 88% yield with a procedure similar to that described
by Thomas et al.[11] Then, a reverse-demand Diels–Alder
reaction with bis(tert-butylphenyl)acetylene (4) under mi-
crowave irradiation gave hexaarylbenzene 5 in 65% yield.
Known tolane 4[12] was obtained in nearly quantitative yield
through a Sonogashira coupling reaction by using con-
trolled microwave heating of ethynyltrimethylsilane
(TMSA) and 1-bromo-4-tert-butylbenzene,[13] deprotection
of the alkyne by NaOH/MeOH/H2O,[14] and again coupling
of obtained 1-tert-butyl-4-ethynylbenzene with 1-bromo-4-
tert-butylbenzene under similar conditions. Then micro-
wave-assisted cyanation[15] of aryl bromide 5 with CuCN in
1-methyl-2-pyrrolidinone (NMP) gave dicyanohexaphenyl-
benzene 6 in 55% yield. The nitrile group was then con-
verted into a diaminotriazine group by reaction with dicy-
andiamide and KOH in 2-methoxyethanol under microwave
irradiation.[16] In a first attempt, even with the use of an
excess amount of dicyandiamide, only the monodiaminotri-
azine compound was isolated. To complete the reaction, ad-
ditional amounts of the reagents (dicyandiamide and KOH)
had to be added, and the mixture required additional irradi-
ation. As a result of its low solubility in 2-methoxyethanol,
bis(diaminotriazine) hexaarylbenzene 1 precipitated and
could be easily isolated by filtration. To avoid contami-
nation of the sample with melamine, which can be produced
by condensation of dicyandiamide under such basic condi-
tions, the solid was thoroughly washed with boiling water
(melamine solubility: 37 gL–1) and sonicated in chloroform.
Compound 1 was then obtained as a white solid; it is
poorly soluble in DMSO and insoluble in other solvents.
The NMR spectroscopic data and mass spectroscopic data
are in accordance with the proposed structure.
Scheme 1. Reagents and conditions: (a) KOH, EtOH, room temp.;
(b) diphenyl ether, microwave, 225 °C; (c) CuCN, NMP, microwave,
220 °C; (d) dicyandiamide, KOH, 2-methoxyethanol, microwave,
225 °C.
tion afforded compound 9, following the general method
described previously.[17] Compound 8 was obtained in five
steps from acenaphthene by Friedel–Crafts acylation with
dimethylcarbamoyl chloride to give acenaphthene-4,5-di-
carboxylic acid-di-N,N-dimethylamide.[18] The two dimeth-
ylamide groups were then hydrolyzed, which after esterifica-
tion, yielded dimethyl acenaphthene-4,5-dicarboxylate.[19]
Monobromination with NBS and dehydrobromination with
LiBr/DMF provided dimethylacenaphthylene-4,5-dicarbox-
ylate.[19] This latter was finally hydrolyzed and dehydrated
to give 8 as an orange powder (see Supporting Infor-
mation).[20]
Attempts were made to convert directly dicarboxylic an-
hydride 8 into its dicarboxylic imide derivative. Methods
described in the literature involving the use of concentrated
NH4OH solution[21] or formamide[22] did not allow the for-
mation of the imide, probably as a result of the low solubil-
ity of compound 8 under these conditions. In this way, the
direct synthesis of half lander 11 from cyclopentadienone 7
could not be achieved.
The synthesis of lander imide 2 is shown in Scheme 2.
The key step is the oxidative cyclodehydrogenation of func-
tionalized 11, which was prepared in two steps from cyclo-
pentadienone 7.[17]
From compound 9, two routes are possible for the syn-
thesis of lander imide 2. The first one consists of the oxidat-
Diels–Alder condensation of cyclopentadienone 7 with ive coupling of precursor 9 to afford lander 10, followed by
dione 8 with concomitant decarbonylation and aromatiza- the formation of imide 2 from the anhydride. The second
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R. Barattin, A. Gourdon
FULL PAPER
Scheme 2. Reagents and conditions: (a) o-xylene, heat; (b) urea, DMF, heat; (c) FeCl3, DCM, room temp.
= 5.30 ppm, δC = 53.8 ppm, [D6]DMSO at δH = 2.52 ppm and δC
= 40.08 ppm}. Mass spectrometry was performed with a Nermag
R10-R10 (DCI). Elemental analyses were done by the Service
d’Analyse de l’ICSN (Paris). THF and ethyl ether were distilled
from Na/benzophenone. Dichloromethane was distilled from cal-
cium hydride. Other solvents and reagents were used as obtained
in the best quality available. Microwave heating was carried out in
closed vials with a CEM-Discover monomode microwave appara-
tus under the conditions (power, temperature, time) given here. Af-
ter completion of the reaction, the vessel was cooled down rapidly
starts with the prior conversion of the anhydride group into
an imide group to afford half lander 11, upon which oxidat-
ive cyclodehydrogenation is performed to obtain lander 2.
Lander anhydride 10 was easily obtained in quantitative
yield from compound 9 by treatment with solid FeCl3 in
dichloromethane.[23] Surprisingly, the use of predissolved
FeCl3 in nitromethane, reported by Müllen et al. on similar
products,[24] led to an undesired mixture of products that
could not be easily purified.
Acenaphthofluorantheneimide 11 was obtained from an- to 60 °C.
hydride 9 in quantitative yield by prolonged heating with
urea in DMF, by modifying the conditions reported by
Kacprzak.[22b] Similar conditions applied to lander anhy-
dride 10 did not allow the formation of lander imide 2. The
conversion seems to be very slow and large amounts of the
starting material were recovered.
Lander imide 2 was finally obtained from half lander
imide 11 by using the oxidative cyclodehydrogenation
method described above. Conversion was not quantitative
and difficult purification by column chromatography was
necessary to afford pure lander 2 as a blue solid. Com-
pound 2 is only poorly soluble and degrades in chloroform.
2,5-Bis(4-bromophenyl)-3,4-bis(4-tert-butylphenyl)cyclopenta-2,4-
dien-1-one (3): To a boiling solution of 1,2-bis(4-tert-butylphenyl)-
ethane-1,2-dione (501 mg, 1.55 mmol) and 1,3-bis(4-bromophenyl)-
acetone (572 mg, 1.55 mmol) in ethanol (5 mL) was added a solu-
tion of KOH (2 , 0.5 mL) in water. The solution was heated at
reflux for 3 h and then cooled to 0 °C. The suspension was filtered,
and the precipitate was washed with cold ethanol and dried in
vacuo to afford compound 3 (891 mg, 1.36 mmol, 88%) as a black
powder. 1H NMR (300 MHz, CD2Cl2): δ = 1.27 (s, 18 H, 6ϫCH3),
6.83 (d, J = 8.6 Hz, 4 H, Ar-H), 7.12 (d, J = 8.7 Hz, 4 H, Ar-H),
7.21 (d, J = 8.6 Hz, 4 H, Ar-H), 7.39 (d, J = 8.7 Hz, 4 H, Ar-H)
ppm. 13C NMR (75 MHz, CD2Cl2): δ = 30.9 (CH3), 34.6 (C), 121.5
(C), 124.0 (C), 124.9 (CH), 128.9 (CH), 129.7 (C), 130.2 (C), 131.1
(CH), 131.7 (CH), 152.3 (C), 155.5 (C), 199.6 (C) ppm. MS (DC/
NH3): m/z (%) = 655 (100) [M + H]+, 672 [M + NH4]+. C37H34Br2O
(654.47): calcd. C 67.90, H 5.24; found C 67.02, H, 4.89.
Conclusions
1,4-Bis(4-bromophenyl)-2,3,5,6-tetrakis(4-tert-butylphenyl)benzene
(5): A mixture of compound 3 (800 mg, 1.22 mmol) and bis(tert-
butylphenyl)acetylene 4 (354 mg, 1.22 mmol) in diphenyl ether (6 g)
was subjected to microwave irradiation (300 W) for 45 min at
250 °C. After cooling, the solution was diluted with CH2Cl2
(25 mL) and poured into methanol (100 mL). The suspension was
filtered, and the precipitate was washed with methanol and vacuum
dried to afford compound 5 (731 mg, 65%) as a white solid. It can
be further purified by column chromatography (hexane/CH2Cl2,
3:2). 1H NMR (300 MHz, CDCl3): δ = 1.12 (s, 36 H, 12ϫCH3),
6.63 (d, J = 8.4 Hz, 8 H, Ar-H), 6.70 (d, J = 8.4 Hz, 4 H, Ar-H),
In summary, we prepared two complementary molecular
moulds for self-assembly on surfaces. Further work is now
underway to use these moulds for the bottom-up fabrica-
tion of metallic wires on insulators
Experimental Section
General Methods: 1D and 2D 1H and 13C NMR spectra were re-
corded with a Bruker Avance-300 in solutions at 20 °C and internal
standard {CDCl3 at δH = 7.25 ppm, δC = 77.0 ppm, CD2Cl2 at δH 6.84 (d, J = 8.4 Hz, 8 H, Ar-H), 6.96 (d, J = 8.4 Hz, 4 H, Ar-H)
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Synthesis of Two Complementary Molecular Moulds
ppm. 13C NMR (75 MHz, CDCl3): δ = 31.2 (CH3), 34.1 (C), 119.2 added iron(III) chloride (120 mg, 0.740 mmol). The violet mixture
(C), 123.4 (CH), 129.6 (CH), 130.9 (CH), 133.1 (CH), 137.2 (C), was stirred for 1.5 h at room temperature under a slow flow of
139.0 (C), 139.9 (C), 140.5 (C), 147.9 (C) ppm. MS (DC/NH3): m/z argon. Another aliquot of FeCl3 (120 mg, 0.740 mmol) was added.
(%) = 935 (100) [M + NH4]+. C58H60Br2 (916.90): calcd. C 75.98,
H 6.60; found C 76.1, H 6.34.
After stirring for 2 h, more FeCl3 (165 mg, 1.020 mmol) was finally
added and stirring was continued overnight at room temperature
(solution became blue). Methanol (20 mL) was added to quench
the reaction. After filtration under vacuum, the blue solid was thor-
oughly washed with methanol and hot ethanol. The blue solid was
then dissolved in chloroform and precipitated in pentane. After fil-
1,4-Bis(4-cyanophenyl)-2,3,5,6-tetrakis(4-tert-butylphenyl)benzene
(6): A mixture of compound 5 (450 mg, 0.49 mmol) and CuCN
(120 mg, 1.35 mmol) in NMP (6 mL) was subjected to microwave
irradiation (300 W) for 15 min at 220 °C. After irradiation, the mix-
ture was cooled to room temperature and poured into ice water.
The precipitate was filtered and washed successively with aqueous
ammonia and water. The crude product was taken up in chloro-
form and filtered through Celite. After removal of the solvent under
reduced pressure, the crude product was purified by column
chromatography (cyclohexane/CHCl3, 1:1) to afford compound 6
1
tration, lander 10 (99 mg, 95%) was obtained as a blue solid. H
NMR (300 MHz, CDCl3): δ = 1.42 (s, 72 H, 24ϫCH3), 6.76 (d, J
= 4.7 Hz, 4 H, Ar-H), 6.80 (d, J = 4.7 Hz, 4 H, Ar-H), 7.51 (s, 8
H, Ar-H), 7.74 (s, 4 H, Ar-H), 7.93 (d, J = 5.1 Hz, 4 H, Ar-H),
8.21 (d, J = 4.5 Hz, 4 H, Ar-H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 31.6, 35.3, 117.0, 122.0, 122.5, 122.9, 122.9, 123.5, 125.1, 127.0,
131.0, 132.3, 134.3, 134.6, 136.3, 137.0, 137.2, 137.5, 139.2, 144.0,
152.5, 160.3 ppm. MS (DC/NH3): m/z (%) = 1543 (100) [M + H]+.
C112H100O6 (1542.04): calcd. C 87.24, H 6.54; found C 86.81, H
6.34.
1
(220 mg, 55%) as a white solid. H NMR (300 MHz, CDCl3): δ =
1.11 (s, 36 H, 12ϫCH3), 6.61 (d, J = 8.45 Hz, 8 H, Ar-H), 6.84 (d,
J = 8.45 Hz, 8 H, Ar-H), 6.94 (d, J = 8.5 Hz, 4 H, Ar-H), 7.15 (d,
J = 8.5 Hz, 4 H, Ar-H) ppm. 13C NMR (75 MHz, CDCl3): δ =
31.1 (CH3), 34.1 (C), 108.8 (C), 119.3 (C), 123.6 (CH), 130.4 (CH),
130.8 (CH), 132.1 (CH), 136.4 (C), 139.1 (C), 140.4 (C), 146.2 (C),
148.6 (C) ppm. MS (DC/NH3): m/z (%) = 827 (100) [M + NH4]+.
C60H60N2 (809.13): calcd. C 89.06, H 7.47, N 3.46; found C 89.36,
H 7.59, N 3.05.
Half Lander Dicarboxylic Imide (11): A suspension of compound
9 (200 mg, 0.26 mmol) and urea (326 mg, 5.43 mmol) in dry DMF
(4 mL) was heated at reflux under an atmosphere of argon for 20 h.
After cooling to room temperature, the mixture was filtered and the
resultant orange solid was washed with water and dried in vacuo to
afford compound 11 (199 mg, quant.). 1H NMR (300 MHz,
CDCl3): δ = 1.43 (s, 36 H, 12ϫCH3), 6.74 (d, J = 7.5 Hz, 2 H, Ar-
H), 6.88 (d, J = 7.1 Hz, 2 H, Ar-H), 7.37 (dd, 2 H, Ar-H), 7.53 (d,
J = 1.8 Hz, 4 H, Ar-H), 7.73 (t, J = 1.8 Hz, 2 H, Ar-H), 7.78 (d, J
= 8.2 Hz, 2 H, Ar-H), 8.15 (d, J = 7.5 Hz, 2 H, Ar-H), 8.25 (s, 1
H, NH) ppm. 13C NMR (75 MHz, CDCl3): δ = 31.5 (CH3), 35.3
(C), 121.1 (C), 121.7 (CH), 123.1 (CH), 123.2 (CH), 124.1 (CH),
126.3 (C), 127.2 (CH), 127.8 (CH), 129.6 (C), 131.8 (CH), 132.7
(C), 133.2 (C), 135.9 (C), 136.8 (C), 136.9 (C), 137.4 (C), 138.9 (C),
143.4 (C), 152.4 (C), 163.8 (C) ppm. MS (DC/NH3): m/z (%) = 772
(100) [M + H]+. C56H53NO2 (771.41): calcd. C 87.12, H 6.92, H
1.81; found C 86.52, H 6.39.
1,4-Bis[4-(3,5-diamino-2,4,6-triazine)phenyl]-2,3,5,6-tetrakis(4-tert-
butylphenyl)benzene (1):
A mixture of compound 8 (84 mg,
0.104 mmol), dicyandiamide (108 mg, 1.28 mmol) and powdered
KOH (25 mg, 0.45 mmol) in 2-methoxyethanol (2.5 mL) was sub-
jected to microwave irradiation (300 W) for 15 min at 225 °C. After
cooling, dicyandiamide (112 mg, 1.34 mmol) and powdered KOH
(23 mg, 0.40 mmol) were added and irradiation was continued for
15 min at 225 °C. The resulting mixture was cooled, diluted with
boiling water (30 mL) and filtered. The solid was extracted thor-
oughly with hot water, washed with chloroform and dried in vacuo
to afford compound 1 (63 mg, 62%) as a white solid. It can be
further purified by crystallization from acetic acid. 1H NMR
(300 MHz, CDCl3): δ = 1.03 (s, 36 H, 12ϫCH3), 6.56 (s, 8 H,
NH2), 6.71 (d, J = 4.8 Hz, 8 H, Ar-H), 6.81 (d, J = 4.8 Hz, 8 H,
Ar-H), 6.99 (d, J = 5.1 Hz, 4 H, Ar-H), 7.72 (d, J = 5.1 Hz, 4 H,
Ar-H) ppm. 13C NMR data not recorded for solubility reasons.
MS (DC/NH3): m/z (%) = 978 (100) [M + H]+. C64H68N10 (977.29):
calcd. C 78.65, H 7.01, N 14.33; found C 78.45, H 7.11, N 14.53.
Lander Dicarboxylic Imide (2): To a degassed solution of half
lander imide 11 (86 mg, 0.111 mmol) in dry dichloromethane
(11 mL) was added iron(III) chloride (100 mg, 0.620 mmol). The
violet mixture was stirred for 1 h at room temperature under a slow
flow of argon. Another aliquot of FeCl3 (120 mg, 0.740 mmol) was
added. After stirring for 2 h, more FeCl3 (150 mg, 0.925 mmol) was
finally added and stirring was continued overnight at room tem-
perature (solution became blue). Methanol (20 mL) was added to
quench the reaction. After filtration under vacuum, the blue solid
was thoroughly washed with methanol and hot ethanol. The blue
solid was then purified by column chromatography (CHCl3/MeOH,
9.7:0.3); the product was then dissolved in a minimum volume of
chloroform and precipitated by the addition of methanol or pen-
tane. Yield: 18%. The product is only poorly soluble in chloroform
Half Lander Dicarboxylic Anhydride (9): A mixture of cyclopen-
tadienone 7 (154 mg, 0.265 mmol) and dicarboxylic anhydride 8
(57 mg, 0.256 mmol) in o-xylene (2 mL) was subjected to micro-
wave irradiation (300 W) for 40 min at 210 °C. The resulting mix-
ture was cooled, diluted with dichloromethane (30 mL) and con-
centrated in vacuo. The residue was purified by column chromatog-
raphy (dichloromethane/petroleum ether, 7:3) to afford anhydride
9 (103 mg, 52%) as an orange solid. 1H NMR (300 MHz, CDCl3):
δ = 1.43 (s, 36 H, 12ϫCH3), 6.78 (d, J = 7.48 Hz, 2 H, Ar-H), 6.89
(d, J = 7.1 Hz, 2 H, Ar-H), 7.39 (dd, 2 H, Ar-H), 7.52 (d, J =
1.8 Hz, 4 H, Ar-H), 7.74 (t, J = 1.8 Hz, 2 H, Ar-H), 7.81 (d, J =
8.1 Hz, 2 H, Ar-H), 8.22 (d, J = 7.48 Hz, 2 H, Ar-H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 31.5 (CH3), 35.3 (C), 117.3 (C), 121.9
(CH), 123.0 (CH), 123.5 (CH), 124.3 (CH), 127.0 (C), 127.4 (CH),
127.9 (CH), 129.6 (C), 132.3 (C), 133.2 (C), 134.3 (CH), 135.7 (C),
136.6 (C), 137.2 (2 C), 139.3 (C), 144.2 (C), 152.5 (C), 160.3 (C)
ppm. MS (DC/NH3): m/z (%) = 791 (100) [M + NH4]+. C56H52O3
(773.01): calcd. C 87.01, H 6.78; found C 87.36, H 7.01.
1
and degrades in solution. H NMR (300 MHz, CDCl3) (low solu-
bility, broad peaks, unstable in CDCl3): δ = 1.43 (s, 72 H,
24ϫCH3), 6.76 (d, J = 9 Hz, 4 H, Ar-H), 7.52 (s, 8 H, Ar-H), 7.73
(s, 4 H, Ar-H), 7.92 (d, J = 7 Hz, 4 H, Ar-H), 8.08–8.16 (m, 8 H,
Ar-H) ppm; main impurities at saturation: residual solvent. 13C
NMR not recorded for solubility and stability reasons.
C112H102N2O4 (1540.07): calcd. C 87.35, H 6.68, N 1.82; found C
87.01, H 7.34, N 1.67.
Supporting Information (see footnote on the first page of this arti-
cle): 1H and 13C NMR spectra for new compounds 1–3, 5, 6, 9–
11. Synthesis and characterization data of compound 8.
Lander Dicarboxylic Anhydride (10): To a degassed solution of an-
hydride 9 (104 mg, 0.134 mmol) in dry dichloromethane (8 mL) was
Eur. J. Org. Chem. 2009, 1022–1026
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R. Barattin, A. Gourdon
FULL PAPER
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Received: September 30, 2008
Published Online: January 14, 2009
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