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(silica gel, ethyl acetate/petroleum
ether=1/4, v/v) to give the pure
CATP2 (0.20 g, 87%). 1HNMR
(400 MHz, CDCl3): d=8.25 (14H,
m), 7.53 (4H, d, J=8.0 Hz), 6.64
(12H, m), 3.32 (8H, m), 1.23 (16H,
m), 0.91 ppm (12H, m). 13CNMR
(100 MHz, CDCl3): d=195.4, 167.4,
153.7, 153.3, 151.4, 150.8, 136.7,
135.6, 134.6, 134.0, 132.8, 132.0,
131.7, 131.2, 130.6, 129.8, 129.3,
128.5, 128.3, 126.1, 125.0, 123.0,
122.8, 114.6, 113.1, 112.4, 111.9,
93.3, 65.2, 50.8, 31.6, 30.2, 29.3,
29.1, 19.9, 18.8, 13.5, 13.4 ppm. FT-
Figure 4. Open-aperture Z-scans measured in a THF solution of: a) ATP and b) CATP1, CATP2. As seen from the
figures, the optical transmission is a function of the sample option (Z=0 is the beam focus). Tnorm is the measured
transmission normalized by the linear transmission of the sample. The solid curves correspond to numerical fits to
the data.
~
IR (KBr): n=2927, 2867, 2216,
1660, 1485, 1186, 833 cmꢀ1
.
mixture was heated to 708C and N,N-dibuty-4-ethynylaniline
(0.47 g, 2.04 mmol, 2 equiv) was injected. After 15 min of stirring at
this temperature, the reaction was continually heated to 808C and
stirred for 8 h under argon atmosphere. The cooled reaction mix-
ture was diluted with CH2Cl2 and extracted with water. The organic
phase was dried with MgSO4 and the solvent was removed under
reduced pressure. The crude product was purified by column chro-
matography (silica gel, dichloromethane/petroleum ether=1/4, v/
v) to give ATP (0.52 g, 65%). 1HNMR (400 MHz, CDCl3): d=8.98
(1H, s), 8.71 (2H, s), 8.10 (11H, m), 7.65 (4H, d, J=8.0 Hz), 6.60 (4H,
d, J=8.0 Hz), 3.29 (8H, m), 1.30 (16H, m), 0.96 ppm (12H, m).
13CNMR (100 MHz, CDCl3): d=195.6, 137.1, 132.9, 132.4, 131.0,
130.6, 129.8, 128.2, 127.9, 127.5, 126.3, 125.9, 125.1, 124.4, 124.2,
MALDI-TOF-MS (dithranol): m/z: calcd. for C81H66N10O:
1194.54 gmolꢀ1, found: 1195.5 gmolꢀ1 [MH]+. Elemental analysis
calcd. (%) for C81H66N10O (1195.46): C 81.37, H 5.52, N 11.69; found:
C 81.38, H 5.56, N 11.72. MP: 1988C.
Nonlinear Optical Studies: Z-Scan Measurement
In our experiments, to investigate the third-order nonlinearities of
the products, Z-scan measurements were performed using a 20 ps
mode-locked Nd:YAG laser at 532 nm. “Open aperture” Z-scan
measurements were carried out to separately determine the imagi-
nary part of the third-order nonlinear susceptibility c(3) and the
nonlinear absorption coefficient b, which is related to the nonlinear
absorption of the samples. Additionally, the advantage of the Z-
scan measurements is that apart from the magnitude, they can
also provide the sign of Imc(3), where the latter is directly related
to the nonlinear absorption type [saturable absorption (SA) or re-
verse saturable absorption (RSA)].
~
122.9, 121.9, 111.0, 50.4, 29.4, 29.1, 20.0, 13.7 ppm. FTIR (KBr): n=
2960, 2874, 2150, 1605, 1514, 1365, 1178, 860, 818 cmꢀ1. MALDI-
TOF-MS (dithranol): m/z: calcd. for C57H58N2O: 786.45 gmolꢀ1
,
found: 787.1 gmolꢀ1 [MH]+. Elemental analysis calcd. (%) for
C57H58N2O (787.08): C 86.97, H 7.37, N 3.55; found: C 86.98, H 7.43,
N 3.56. MP: 1418C.
Details of the experimental techniques, as well as the procedure to
analyze the experimental data, are only briefly described here. Ex-
tended information can be found in the literature. Here, a laser
beam is focused using a lens and passed through the sample. The
beam’s propagation direction is taken as the z axis, and the focal
point is taken as Z=0. The beam will have a maximum energy
density at the focus, which will symmetrically reduce toward either
side for the positive and negative values of Z. In our experiments,
THF solutions of the samples were taken in 1 mm cuvettes and the
measurements were performed by placing the samples in the
beam at different positions with respect to the focus (different
values of z) and measuring the corresponding light transmission.
The graph plotted between the samples T (norm) (transmission
normalized to the linear transmission of the sample) is known as
the Z-scan curve. From the “open aperture” Z-scan curves, the non-
linear absorption coefficient b was determined using Equation (1):
Synthesis of 3, 3’-(10-benzoyltriphenylene-2,6-diyl)bis(2-(4-(di-
butylamino)phenyl)buta-1,3-di-ene-1,1,4,4-tetracarbonitrile)
(CATP1): ATP (0.15 g, 0.20 mmol, 1 equiv) and TCNE (51.2 mg,
0.40 mmol, 2 equiv) were mixed in dichloromethane (10 mL). After
stirring for several minutes, the solvent was removed under re-
duced pressure and the crude product was purified by column
chromatography (silica gel, ethyl acetate/petroleum ether=1/4, v/
v) to give the final click-type reaction product CATP1 (0.18 g,
1
89%). HNMR (400 MHz, CDCl3): d=8.23 (14H, m), 7.47 (4H, d, J=
8.0 Hz), 6.60 (4H, d, J=8.0 Hz), 3.29 (8H, m), 1.36 (16H, m),
0.96 ppm (12H, m). 13CNMR (100 MHz, CDCl3): d=195.7, 167.6,
153.9, 153.4, 151.6, 150.9, 136.9, 135.7, 134.8, 134.1, 133.9, 133.0,
130.2, 131.2, 130.6, 128.8, 128.3, 126.1, 125.0, 123.0, 122.8, 114.6,
113.1, 112.1, 111.9, 93.3, 65.2, 51.3, 31.6, 30.2, 29.8, 29.5, 20.4,
~
14.0 ppm. FTIR (KBr): n=2927, 2867, 2216, 1660, 1485, 1186,
818 cmꢀ1. MALDI-TOF-MS (dithranol): m/z: calcd. for C69H58N10O:
1042.48 gmolꢀ1, found: 1043.3 gmolꢀ1 [MH]+. Elemental analysis
calcd. (%) for C69H58N10O (1043.27): C 79.36, H 5.56, N 13.42; found:
C 79.44, H 5.60, N 13.43. MP: 1858C.
pffiffiffi
2
2½1 ꢀ TðZ ¼ 0Þꢁ
bðm wꢀ1Þ ¼
ð1Þ
I0Leff
Synthesis of 2,2’-(2,2’-(10-benzoyltriphenylene-2,6-diyl)bis(1-(4-
(dibutylamino)phenyl)-2-(4-(dicyanomethylene) cyclohexa-2,5-di-
enylidene)ethan-2-yl-1-ylidene))dimalononi trile (CATP2): ATP
(0.15 g, 0.20 mmol, 1 equiv) and TCNQ (0.08 g, 0.40 mmol, 2 equiv)
were dissolved in dichlorobenzene (10 mL). Under stirring, the re-
actor was heated to 1408C and maintained for 1 h. The solvent of
the cooled reaction mixture was removed under reduced pressure
and the crude product was purified by column chromatography
where T is the normalized transmittance, Leff ¼ ð1 ꢀ expðꢀa0LÞÞ=a0
is the effective thickness of the sample, a0 is the linear absorption
coefficient of the sample at the laser excitation wavelength, L is
the sample thickness, and I0 is the on-axis irradiance at the focus.
The beam waist w0 at the Z=0 was 12.6 mm, the parameter Z0 was
0.94, the pulse repetition rate of the laser was 10 Hz, and the I0 in-
tensity was 3.11 GWcmꢀ2. From the nonlinear absorption coeffi-
cient, the imaginary part of the third-order nonlinear susceptibility
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ChemPhysChem 2013, 14, 4102 – 4108 4107