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Figure 6. Calculated frontier molecular orbital profiles and energy levels for 1a/1b and 2a/2b. The long alkoxy chains in 1b and 2b were replaced by ethoxy
groups to reduce the calculation cost and time.
7.71 (d, J=8.4 Hz, 2H), 7.67 (t, J=8.5 Hz, 2H), 7.61 (d, J=8.4 Hz,
2H), 7.38 (dd, J=8.4, 7.4 Hz, 1H), 7.27 (m, 3H), 7.15 (d, J=8.4 Hz,
1H), 6.99 (dd, J=8.5, 1.7 Hz, 4H), 5.98 (s, 2H), 3.83 (td, J=6.6,
Due to the extended p-conjugation, large TPA cross-sections
were obtained, and thus these materials represent new high-
performance NIR dyes and TPA chromophores for applications
such as NIR photodetection and light saturation at telecommu-
nication wavelengths. Our research provides guidance for ob-
taining NIR dyes with very intense absorption at longer wave-
lengths in the NIR region. Experiments aimed at further ex-
tending the p-conjugated system based on this concept are
currently underway.
3.7 Hz, 8H), 1.49 (s, 9H), 1.17 (s, 18H), 1.12--0.35 ppm (m, 92H);
13C NMR (126 MHz): d=160.11, 160.07, 151.34, 150.66, 150.57,
149.96, 149.39, 139.19, 137.94, 137.69, 136.75, 133.80, 132.43,
131.71, 131.63, 131.45, 131.21, 131.13, 130.30, 129.99, 129.57,
128.18, 125.29, 125.17, 124.67, 124.56, 121.73, 121.57, 121.53,
119.68, 118.00, 117.78, 117.50, 112.82, 105.33, 105.27, 68.69, 68.53,
34.74, 34.68, 31.83, 31.82, 31.53, 31.44, 31.36, 30.21, 29.69, 29.44,
29.43, 29.33, 29.22, 29.21, 29.17, 29.02, 29.00, 28.66, 28.62, 28.58,
28.47, 25.13, 25.07, 22.60, 14.06, 14.05 ppm; HRMS (APCI): m/z=
1859.1759 (M++1); elemental analysis calcd (%) for C125H160N5O4Zn:
1859.1756 (error= +0.2 ppm).
Experimental Section
Synthesis of compounds 5a/5b
General procedure for the synthesis of diporphyrins 1a/1b/
2a/2b
Perylene 3 (271.5 mg, 0.4 mmol), porphyrin 4a/4b (0.4 mmol),
Pd(PPh3)4 (46 mg, 0.04 mmol), and Cs2CO3 (260 mg, 0.8 mmol) were
dried under vacuum and then purged with argon. Degassed tolu-
ene (10 mL) and DMF (5 mL) were then added, and the mixture
was stirred at 968C for 36 h. After cooling, water was added and
the product was extracted with CH2Cl2 (3ꢀ30 mL). The organic
layer was washed with saturated brine and dried over anhydrous
Na2SO4. The solvent was removed under vacuum, and the residue
was purified by column chromatography (silica gel; CH2Cl2/hexane,
1:3) to give the coupling product 5a/5b as a purple solid.
Argon was bubbled through a solution of porphyrin-NP dyad 5a/
5b (50 mg) in dry toluene (25 mL) for 10 min and then DDQ
(5 equiv) and Sc(OTf)3 (5 equiv) were added. The reaction mixture
was heated and stirred under Ar for some additional time (508C
for 2 h for diporphyrins 2a/2b; 908C for 5 h for diporphyrins 1a/
1b). THF (5 mL) was then added to quench the reaction and the
mixture was stirred for a further 1 h. The mixture was then passed
through a short neutral alumina column and the solvent was re-
moved. The residue was further purified on a second neutral alumi-
na column (THF/CH2Cl2, 1:1, as eluent). After washing with MeOH,
the porphyrin dimers 2a/2b and 1a/1b were obtained as dark-
purple solids.
1a: Yield: 19%; 1H NMR (400 MHz, CDCl3): d=9.18–8.91 (m, 4H),
8.86 (br, 2H), 8.73 (br, 2H), 8.53 (br, 2H), 8.25 (d, 2H), 8.05 (br, 2H),
7.88 (m, 2H), 7.75 (br, 4H), 7.64 (s, 4H), 7.59 (s, 4H), 7.37 (br, 4H),
7.23–7.12 (m, 5H), 6.97 (s, 2H), 6.93 (s, 2H), 5.99 (s, 4H), 2.59 (d, J=
17.2 Hz, 12H), 2.13 (s, 24H), 1.45 (s, 18H), 1.17 ppm (s, 36H); HRMS
(MALDI-TOF): m/z=2400.9882 (M+); elemental analysis calcd (%)
for C166H140N10Zn2: 2400.9840 (error= +1.75 ppm).
1
5a:[16c] Yield: 75%; H NMR (CDCl3, 400 MHz): d=10.21 (s, 1H), 9.37
(d, J=4.5 Hz, 2H), 8.93 (d, J=4.4 Hz, 2H), 8.77 (m, 3H), 8.69 (m,
3H), 8.54 (s, 1H), 8.30 (d, J=8.4 Hz, 1H), 7.88 (dd, J=15.1, 6.9 Hz,
2H), 7.73 (d, J=8.1 Hz, 2H), 7.63 (d, J=8.2 Hz, 2H), 7.46 (m, 1H),
7.30--7.21 (m, 8H), 5.98 (s, 2H), 2.63 (s, 6H), 1.89 (s, 6H), 1.83 (s,
6H), 1.49 (s, 9H), 1.12 ppm (s, 18H); 13C NMR (100 MHz, CHCl3): d=
151.37, 151.10, 150.07, 149.99, 149.91, 149.69, 139.29, 139.08,
138.92, 138.02, 137.43, 137.06, 136.59, 133.56, 132.61, 132.53,
132.37, 132.06, 131.31, 131.21, 130.83, 130.39, 129.99, 128.20,
127.68, 127.61, 126.57, 125.35, 125.15, 124.77, 124.41, 123.47,
121.94, 121.68, 121.23, 120.50, 120.28, 118.92, 118.74, 117.98,
117.34, 114.71, 105.41, 50.41, 34.70, 31.53, 31.32, 21.75, 21.62,
21.45 ppm; HRMS (APCI): m/z=1206.5387 (M++1); elemental anal-
ysis calcd (%) for C83H76N5Zn: 1206.5399 (error=ꢀ1.0 ppm).
1b: Yield: 17%; 1H NMR (400 MHz, C6D6): d=8.73 (d, J=7.9 Hz,
2H), 8.72 (s, 2H), 8.64 (d, J=7.2 Hz, 2H), 8.56 (d, J=5.5 Hz, 2H),
8.42 (d, J=7.9 Hz, 2H), 8.37 (d, J=8.1 Hz, 2H), 8.10 (m, 2H), 7.94
(d, J=4.3 Hz, 2H), 7.77 (d, J=7.1 Hz, 4H), 7.70 (m, 2H), 7.59 (s, 2H),
7.58 (s, 2H), 7.54 (d, J=8.1 Hz, 4H), 7.52–7.42 (m, 12H), 6.78 (dd,
J=13.5, 8.6 Hz, 8H), 5.57 (s, 4H), 3.86 (m, 16H), 1.38 (s, 18H), 1.30
(s, 36H), 1.25–0.65 ppm (m, 184H); HRMS (MALDI-TOF): m/z=
5b: Yield: 69%; 1H NMR (500 MHz): d=10.14 (s, 1H), 9.31 (d, J=
4.5 Hz, 2H), 9.03 (d, J=4.4 Hz, 2H), 8.78 (d, J=4.6 Hz, 2H), 8.76 (s,
1H), 8.75 (d, J=4.6 Hz, 2H), 8.66 (s, 1H), 8.65 (d, J=7.6 Hz, 1H),
8.28 (d, J=8.5 Hz, 1H), 7.85 (dd, J=8.5, 7.4 Hz, 1H), 7.83 (s, 1H),
&
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Chem. Eur. J. 2015, 21, 1 – 9
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