D. Fichou et al.
3J
(H,H)=6.6 Hz, 6H), 1.89 (sext, 3J
(H,H)=7.5 Hz, 9H); 13C NMR (75 MHz, CDCl3): d=159.4, 146.8, 142.9,
139.6, 131.7, 128.8, 124.8, 122.7, 103.7, 70.4, 22.9, 11.0 ppm; UV/Vis
(CHCl3): lmax (e)=296 (64250), 318 (80000), 378 (21440), 395 nm
(16440mꢀ1 cmꢀ1); MS (CI): m/z (%): 658.2 (100) [M+H]+, 660.3 (87); el-
emental analysis calcd (%) for C36H30Cl3N3O3: C 65.61, H 4.59, N 6.38;
found: C 65.79, H 4.32, N 6.41.
G
(H,H)=2.7, 9.3 Hz, 3H), 4.11 (t, 3J-
ACHTUNGTRENNUNG
chlorinated (TrisK-Cl-OCn) or non-chlorinated (TrisK-H-
OCn) alkoxy-substituted derivatives (OCnH2n+1 with n=3,
10, 12 and 16), thus allowing for greater versatility in the
control of structure–property relationships. The electronic
properties of the various TrisK compounds have been char-
acterised in solution by means of absorption and emission
spectroscopies and cyclic voltammetry. The crystal structure
of propyloxy-substituted derivative TrisK-H-OC3 has been
determined by X-ray diffraction analysis, which revealed the
existence of stabilising weak intermolecular hydrogen
bonds. Scanning tunnelling microscopy (STM) at the liquid/
solid interface has demonstrated the remarkable 2D self-as-
sembling properties of the TrisK compounds. In particular,
it has revealed that TrisK-H-C12, bearing three dodecyl
chains, forms three different self-organised 2D phases with
row-packing arrangements. Individual molecules can be
imaged with spectacular intramolecular resolution, thus pro-
viding the possibility of correlating the STM features with
calculated charge density distributions.
E
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
6,12,18-Trichloro-2,8,14-tridecyloxy-5,11,17-triazatrinaphthylene
TrisK-
Cl-OC10: The title compound was obtained from 1,3,5-tris(2-carboxy-4-
decyloxyphenylamino)benzene 6b (485.0 mg, 0.5 mmol, 1.0 equiv) after
purification by column chromatography on silica gel (CH2Cl2) as a pale-
yellow solid (410.0 mg, 84%). Rf =0.85 (CH2Cl2); m.p. 90–928C;
1H NMR (300 MHz, CDCl3): d=8.11 (d, 3J
3J(H,H)=2.4 Hz, 3H), 7.42 (dd, 3J
(H,H)=6.6 Hz, 6H), 1.85 (quint, 3J
0.82 ppm (t, 3J(H,H)=6.6 Hz, 9H); 13C NMR (75 MHz, CDCl3): d=
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
159.3, 146.7, 142.8, 139.5, 131.6, 128.7, 124.6, 122.6, 103.6, 68.9, 32.3,
30.04, 30.02, 29.9, 29.77, 29.60, 26.55, 23.1, 14.5 ppm; UV/Vis (CHCl3):
lmax (e)=296 (56650), 317 (70600), 376 (19080), 396 nm
(14600mꢀ1 cmꢀ1); MS (CI): m/z (%): 954.8 (100) [M+H]+, 952.8 (93.4);
elemental analysis calcd (%) for C57H72Cl3N3O3: C 71.8, H 7.61, N 4.41;
found: C 71.59, H 7.42, N 4.54.
6,12,18-Trichloro-2,8,14-tridodecyloxy-5,11,17-triazatrinaphthylene TrisK-
Cl-OC12: The title compound was obtained from 1,3,5-tris(2-carboxy-4-
dodecyloxyphenylamino)benzene 6c (640.0 mg, 0.62 mmol, 1.0 equiv)
after purification by column chromatography on silica gel (CH2Cl2) as a
pale-yellow solid (530.0 mg, 82%). Rf =1.00 (CH2Cl2); m.p. 103–1068C;
Experimental Section
Chemistry, general procedures: 1H and 13C NMR spectra were recorded
on a Bruker Avance 300 spectrometer by using TMS as an internal stand-
ard. Deuterated solvents (CDCl3, [D6]DMSO, CD3OD) were purchased
from SDS. Mass spectrometry services were provided by the Service de
spectromꢀtrie de masse (Dꢀpartement de Chimie, Ecole Normale Supꢀr-
ieure, Paris) and by the I.C.S.N. (Institut de Chimie des Substances Na-
turelles, Gif-sur-Yvette). High-resolution mass spectrometric analyses
were provided by the I.C.S.N. The following abbreviations are used:
chemical ionisation (CI), electrospray ionisation (ESI), time of flight
(TOF), fast-atom bombardment (FAB), matrix-assisted laser desorption
ionisation (MALDI). Melting points (uncorrected) were determined with
an Electrothermal 9100 instrument. TLC analysis was carried out on
silica gel (Merck 60F254) with visualisation at 254 and 366 nm. Preparative
flash chromatography was carried out with Merck silica gel (Si 60, 40–
63 mm). Reagents and chemicals were purchased from Sigma–Aldrich
unless otherwise stated. Solvents were purchased from SDS. Dichlorome-
thane (CH2Cl2), chloroform (CHCl3), and methanol (MeOH) were distil-
led from calcium hydride; toluene and THF were distilled from sodium,
DMF was distilled over MgSO4, pentanol over K2CO3, and acetic acid
from acetic anhydride/CrO3. UV/Vis absorption spectra were recorded
on a Secoman Uvikon XL spectrophotometer; fluorescence emission
spectra were recorded on a Jobin Yvon FluoroMax-3 spectrophotometer
at 208C.
1H NMR (300 MHz, CDCl3): d=8.24 (d, 3J
3J(H,H)=2.7 Hz, 3H), 7.55 (dd, 3J(H,H)=2.7, 9.0 Hz, 3H), 4.26 (t, 3J-
(H,H)=6.6 Hz, 6H), 1.97 (t, 3J
(H,H)=6.6 Hz, 6H), 1.45 (m, 54H),
0.92 ppm (t, 3J(H,H)=6.6 Hz, 9H); 13C NMR (75 MHz, CDCl3): d=
ACHTUNGERTN(NUNG H,H)=9.0 Hz, 3H), 7.89 (d,
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
159.5, 146.9, 143.0, 139.7, 131.9, 128.9, 125.0, 122.9, 103.8, 69.0, 32.3, 30.0
(2C), 29.84 (2C), 29.76 (2C), 29.53, 26.5, 23.1, 14.5 ppm; UV/Vis
(CHCl3): lmax (e)=296 (49400), 317 (61170), 378 (17000), 396 nm
(12950mꢀ1 cmꢀ1); MS (API): m/z (%): 1039.0 (100) [M+H]+; elemental
analysis calcd (%) for C63H84Cl3N3O3: C 72.92, H 8.16, N 4.05; found: C
71.71, H 8.25, N 3.85.
6,12,18-Trichloro-2,8,14-trihexadecyloxy-5,11,17-triazatrinaphthylene
TrisK-Cl-OC16: The title compound was obtained from 1,3,5-tris(2-car-
boxy-4-hexadecyloxyphenylamino)benzene 6d (1.05 g, 0.83 mmol,
1.0 equiv) after purification by column chromatography on silica gel
(CH2Cl2) as a pale-yellow solid (361.0 mg, 34%). Rf =1.00 (CH2Cl2); m.p.
83–878C; 1H NMR (300 MHz, CDCl3): d=8.12 (d, 3J
(H,H)=9.0 Hz,
3
3H), 7.78 (d, 3J
4.15 (t, 3J
(m, 6H), 1.26 (m, 72H), 0.80 ppm (t, 3J
AHCTUNGTRENNUNG
A
N
A
ACHTUNGERTN(NUNG H,H)=6.6 Hz, 6H), 1.44
(75 MHz, CDCl3): d=159.5, 146.9, 143.0, 139.6, 131.7, 128.9, 124.95,
122.9, 103.8, 69.0, 32.3, 30.1 (7C), 30.02, 29.86, 29.77, 29.55, 26.5, 23.1,
14.5 ppm; UV/Vis (CHCl3): lmax (e)=296 (63700), 317 (80100), 379
(21900), 396 nm (16800mꢀ1 cmꢀ1); MS (EI+): m/z (%): 1205.6 (100)
General procedure for the synthesis of 6,12,18-trichloro-2,8,14-trialkoxy-
5,11,17-triazatrinaphthylene derivatives TrisK-Cl-OCn: The requisite
1,3,5-tris(2-carboxy-4-alkoxyphenylamino)benzene 6a–d (1.0 equiv) was
dried under vacuum at 1108C for 4 h and POCl3 (large excess) was
added. The solution was stirred at reflux under nitrogen for 72 h. After
concentration to dryness, the residue was redissolved in CH2Cl2 and the
solution was slowly poured onto an ice-cooled 15% aqueous NH4OH sol-
ution. The biphasic mixture was separated and the organic layer was
dried over MgSO4, filtered, and concentrated under reduced pressure.
The residue was purified as specified below to afford the respective
6,12,18-trichloro-2,8,14-trialkoxy-5,11,17-triazatrinaphthylene TrisK-Cl-
OCn.
+
+
[M] , 1169.6 (65) [MꢀCl] , 1135.6 (36.5) [Mꢀ2Cl] +, 1101.7 (95.2)
C
C
C
[Mꢀ3Cl] , 980.3 (68.2) [MꢀC16H33] +; elemental analysis calcd (%) for
+
C
C
C75H108Cl3N3O3: C 74.69, H 9.03, N 3.48; found: C 74.61, H 9.11, N 3.51.
General procedure for the synthesis of 2,8,14-trialkoxy-5,11,17-triazatri-
naphthylene derivatives TrisK-H-OCn: LiAlH4 (36.0 equiv) was added in
small portions to
a suspension of 6,12,18-trichloro-2,8,14-trialkoxy-
5,11,17-triazatrinaphthylene TrisK-Cl-OCn (1.0 equiv) in THF. After
heating at reflux for 16 h, the mixture was cooled to 08C, whereupon
H2O and EtOH were successively added. After stirring for 20 min, the
mixture was filtered and the solid residue was washed with CHCl3 until
there was no more discoloration. The filtrate, containing TrisK-H-Cn
along with partially reduced products, was concentrated under reduced
pressure. The residue was suspended in EtOH, a solution of FeCl3·6H2O
(9.0 equiv) in H2O was added, and the mixture was heated to reflux for
16 h. After cooling to RT, 15% aqueous NH4OH was added and the sus-
pension was filtered through Celite. The precipitate was washed with
CH2Cl2, and the filtrate was separated and further extracted with CH2Cl2.
6,12,18-Trichloro-2,8,14-tripropyloxy-5,11,17-triazatrinaphthylene TrisK-
Cl-OC3: The title compound was obtained from 1,3,5-tris(2-carboxy-4-
propyloxyphenylamino)benzene 6a (1.03 g, 1.5 mmol, 1.0 equiv) after pu-
rification by column chromatography on silica gel (CH2Cl2) as a pale-
yellow solid (499.0 mg, 49%). Rf =0.475 (CH2Cl2); m.p. 128–1328C;
1H NMR (300 MHz, CDCl3): d=8.1 (d, 3J
ACTHNUTRGNE(UNG H,H)=9.3 Hz, 3H), 7.75 (d,
14662
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 14654 – 14664