Novel fluorescent dyes with fused perylene tetracarboxlic diimide and BODIPY analogue structures

Article abstract of DOI:10.1021/ol801668r

(Chemical Equation) Two novel fluorescent dyes based on perylene tetracarboxylic diimides and BODIPY were designed and synthesized. Significant features, such as longer wavelength absorption and emission, high fluorescence quantum yields, and strong elect

Full text of DOI:10.1021/ol801668r

Supporting information for:
Novel Fluorescent Dyes with Fused Perylene Tetracarboxylic
Diimide and BODIPY analog structures
Junqian Feng,†,‡ Baolong Liang,† Delou Wang,† Lin Xue,† Xiyou Li †,*
Department of Chemistry, Shandong University, 250100, China; College of
Shandong Policeman, Shandong, China, 250014
Contents
Page S1: Title of the paper, authors along with the contents.
Page S2: 1. General methods.
Page S3: 2. Synthesis and structure characterizations of 1-4 (including the copies of
NMR spectra, Figure S1-S7).
Page S12: 3. Simulated absorption spectra of 3 and 4. (Figure S8-S9)
Page S13: 4. Simulated absorption spectra of 1 and 2. (Figure S10-11)
Page S14: 5. Calculated energy levels and the orbital maps of 1 and 2. (Figure
S12-13)
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1. General Methods
1H NMR spectra were recorded at 300 MHz with the solvent peak as internal
standard (in CDCl3). Electronic absorption spectra were recorded in organic solvents
at room temperature. Fluorescence spectra and the fluorescence lifetime were
measured on a Multifrequency Phase and Modulation Fluorometer with the
excitation at 450 nm. The fluorescence lifetimes were measured with multifrequency
phase modulation method with a scattering sample as standard. Fluorescence
quantum yields are calculated with compound 7 as standard. MALDI-TOF mass
spectra were taken on an ultra-high resolution Fourier transform ion cyclotron
resonance (FT-ICR) mass spectrometer. Electrochemical measurements were carried
out under nitrogen atmosphere on an electrochemical working station. The cell
comprised inlets for a glassy carbon disk working electrode of 2.0 mm in diameter
and a silver-wire counter electrode. The reference electrode was Ag/Ag+, which was
connected to the solution by a Luggin capillary whose tip was placed close to the
working electrode. It was corrected for junction potentials by being referenced
internally to the ferrocenium / ferrocene (Fe+ / Fe) couple [E1/2 (Fe+ / Fe) = 501 mV
vs. SCE]. Typically, a 0.1 mol dm-3 solution of [Bu4N][ClO4] in dichloromethane
containing 0.5 mmol dm-3 of sample was purged with nitrogen for 10 min, then the
voltammograms were recorded at ambient temperature. The scan rate was 20 and 10
mV s-1 for CV and DPV, respectively.
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2. Synthesis and structure characterizations
N-n-Butyl-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic-3,4
-anhydride-9,10-imide (5).
1,6,7,12-Tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-tetracarboxylic dianhydride1
(3.0 g, 3.20 mmol) in toluene (100 mL) was purged with dry nitrogen for 15 min and
then was heated to reflux. To this solution n-butylamine (0.32 mL, 3.2 mmol) in
toluene (10 mL) was slowly added over the course of 30 min. The resulting mixture
was refluxed continuously for another 30 min, and then the volatiles were removed
under reduced pressure. The product was separated from the residue by column
chromatography on silica gel with chloroform as eluent. Repeated chromatography
followed by recrystallization from a mixture of CHCl3 and MeOH gave pure product
1
5 (1.70 g, yield 53.1%): mp. > 300°C; H NMR (300 MHz, CDCl3) δ 8.22 (s, 4H),
7.23 (d , J = 8.35 Hz, 8H), 6.82 (d, J = 8.35 Hz, 8H), 4.11 (t, 2H), 1.65 (m, 2H),
1.40(m, 2H), 1.29 (s, 36H), 0.93 (t, 3H); MALDI-TOF MS(m/z) 1040.5, Calcd for
C68H65NO9 (m/z) 1039.5. Anal. Calcd. for C68H65NO9: C, 78.51; H, 6.30; N, 1.35.
Found: C, 78.39; H, 6.38; N, 1.36.
Compound 3:
A mixture of 5 (1 g, 0.96 mmol), 2-methylquinoline (2 g, 14 mmol) and fresh dried
zinc chloride (0.2 g, 1.5 mmol) by thionyl chloride was heated to 200°C for 3 hours.
The reaction cake was extracted several times with dichloromethane. The combined
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extract was dried over sodium sulfate for overnight and then was evaporated to dry
under reduced pressure. The red solid collected was purified by column
chromatography on silica gel using dichloromethane as eluent. Compound 3 was
afforded as red powder (0.7 g, 63 %): mp. > 300°C; UV-vis (CH2Cl2, ε) 582 nm
(6.33 × 104 L mol-1 cm-1), 423 nm; 1H NMR (300 MHz, CDCl3 ) δ 9.64 (d, 1H), 8.34
(s, 2H), 8.26 (d, 1H), 8.21 (s, 2H), 7.80 (d, 2H), 7.73 (t, 1H), 7.51 (t, 1H), 7.22 (m,
4H), 7.21 (d, 4H), 6.89 (br, 4H), 6.81 (d, 4H), 4.12 (t, 2H), 1.66 (m, 2H), 1.40 (m,
13
2H), 1.31 (s, 36H), 0.94 (t, 3H); C NMR (100 Hz, CDCl3) δ 163.1, 155.5, 155.2,
154.9, 153.0, 152.6, 146.4, 146.0, 139.4, 135.5, 132.5, 132.1, 131.6, 129.3, 127.1,
126.0, 125.6, 124.5, 121.9, 121.3, 120.9, 119.4, 119.2, 119.1, 118.9, 118.6, 117.4,
39.8, 33.8, 31.1, 31.0, 29.7, 19.89, 13.29; IR (KBr) ν [cm-1] 2958 (C-H), 2866 (C-H),
1698 (C=O), 1660 (C=O), 1634 (C=O), 1590 (C=C, perylene ring); MALDI-TOF
MS (m/z) 1165.4, Calcd. For C78H72N2O8 (m/z) 1164.5. Anal. Calcd. For C78H72N2O8:
C, 80.39%; H, 6.23%; N, 2.40%. Found: C, 80.23%; H, 6.32%; N, 2.38%.
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Figure S1. 1H NMR spectrum of 3 in CDCl3
Figure S2. 13C NMR spectrum of 3 in CDCl3
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Compound 4*:
A mixture of 6 (1 g, 1.02 mmol), 2-methylquinoline (3 g, 21 mmol) and fresh direded
zinc chloride (0.4 g, 3.0 mmol) by thionyl chloride was heated to 200 °C for 3 hours.
The reaction cake was extracted several times with dichloromethane. The extract
was dried over anhydrous sodium sulfate for overnight and was evaporated to dry
under reduced pressure to give a red mixture. Which was further purified by column
chromatography on silica gel using dichloromethane as eluent to afford compound 4
as red solid (0.73 g, yield 58%). mp. >300 °C; UV-vis (CH2Cl2, ε) 588 nm (8.43 ×
104 L mol-1 cm-1), 423 nm; 1H NMR (300 MHz, CDCl3 ) δ 9.65 (d, 2H), 8.33 (s, 4H),
8.26 (d, 2H), 7.79 (m, 4H), 7.72 (m, 2H), 7.53 (m, 2H), 7.26 (br, 8H), 6.87(br, 8H),
1.31 (s, 36H); IR (KBr) ν [cm-1] 2959 (C-H), 2866 (C-H), 1632 (C=O), 1571 (C=C,
perylene ring); MALDI-TOF MS (m/z) 1235.5, Calcd. For C84H70N2O8 (m/z) 1234.5.
Anal. Calcd. For C84H70N2O8: C, 81.66%; H, 5.71%; N, 2.27%. Found: C, 81.58%;
H, 5.73%; N, 2.38%.
* Compound 4 failed to give a satisfied 13C NMR spectrum probably because of the
bad solubilities in organic solvents. But the structure and the purity of it have been
proved by the TLC, HPLC, elemental analysis, and 1H NMR spectra.
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Figure S3. 1H NMR spectrum of 4 in CDCl3
Compound 1:
0.5 ml N-Ethyldiisopropylamine and 1 ml BF3· Et2O were added to the solution of
0.2 g compound 3 (0.17 mmol) in 15 ml toluene. The mixture was heated to 60 °C
under the protection of nitrogen and stirred at this temperature for 2.5 hours. The
reaction mixture was then evaporated to dry under reduced pressure. The residues
were purified by column chromatography on silica gel using dichloromethane as
eluent. Compound 1 was afforded as red solid (150 mg, yield 72 %). mp. >300°C;
UV-vis (CH2Cl2, ε): 616 nm (6.37 × 104 L mol-1 cm-1), 377 nm; 1H NMR (300 MHz,
CDCl3 ) δ 9.50 (d, 1H), 8.78 (d, 1H), 8.46 (s, 1H), 8.43 (d, 1H), 8.37 (s, 1H), 8.22 (s,
1H), 8.19 (s, 1H), 7.89 (d, 1H), 7.85 (t, 1H), 7.64 (m, 1H), 7.25 (m, 8H), 6.91-6.78
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(m, 8H), 4.11 (t, 2H), 1.65 (m, 2H), 1.40 (m, 2H), 1.31 (s, 36H), 0.94 (t, 3H); 13C
NMR (100 Hz, CDCl3) δ 181.2, 167.2, 163.4, 156.4, 156.2, 156.0, 155.4, 153.4,
153.2, 152.9, 152.7, 152.3, 147.4, 147.3, 147.0, 146.9, 142.1, 139.8, 132.8, 132.3,
131.7, 128.5, 128.2, 127.6, 127.5, 126.7, 126.6, 126.5, 124.0, 123.9, 123.8, 122.7,
122.6, 121.7, 121.5, 120.8, 120.5, 120.3, 119.8, 119.7, 119.5, 119.4, 119.3, 119.2,
119.1, 118.7, 107.7, 40.4, 34.4, 31.5, 30.2, 20.4, 13.8; IR (KBr) ν [cm-1] 2959 (C-H),
2867 (C-H), 1701 (C=O), 1662 (C=O), 1575 (C=C, perylene ring), 1148 (B-F);
MALDI-TOF MS (m/z) 1212.1, Calcd. For C78H71BF2N2O8 (m/z) 1212.5.
Figure S4. 1H NMR spectrum of 1 in CDCl3
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Figure S5. 13C NMR spectrum of 1 in CDCl3
Compound 2:
1 ml N-Ethyldiisopropylamine and 2 ml BF3· Et2O were added to the solution of 0.2
g compound 4 (0.16 mmol) in 15 ml toluene. The mixture was heated and stirred at
60 °C under nitrogen for 2.5 hours. The reaction mixture was evaporated to dry
under reduced pressure and the residues were purified by column chromatography
on silica gel using dichloromethane as eluent. Compound 1 was collected as red
solid (147 mg, yield 68 %). mp. >300°C; UV-vis (CH2Cl2, ε) 650 nm (8.21 × 104 L
mol-1 cm-1), 382 nm; 1H NMR (300 MHz, CDCl3 ) δ 9.49 (d, 2H), 8.78 (d, 2H), 8.45
(s, 2H), 8.43 (s, 2H), 8.34 (d, 2H), 7.89-7.84 (m, 4H), 7.64 (m, 2H), 7.28 (m, 8H),
6.87 (m, 8H), 1.33 (s, 36H); δ 181.3, 167.3, 156.6, 156.3, 155.8, 155.6, 153.4, 153.3,
153.2, 153.0, 152.3, 147.1, 147.0, 146.9, 142.1, 139.8, 132.4, 131.7, 128.8, 128.7,
128.3, 127.6, 127.5, 126.7, 126.6, 126.5, 124.3, 124.2, 123.9, 121.7, 121.6, 121.5,
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120.9, 120.7, 119.7, 119.5, 119.4, 119.1, 119.0, 118.9, 118.8, 107.7, 34.4, 31.5; IR
(KBr) ν [cm-1] 2959 (C-H), 2867 (C-H), 1633 (C=O), 1573 (C=C, perylene ring),
1144 (B-F); MALDI-TOF MS (m/z) 1330.0, Calcd. For C84H68B2F4N2O8 (m/z)
1330.5.
1
Figure S6. H NMR spectrum of 2 in chloroform-d1 recorded (A) on a 300 MHz
instrument, (B) on a 600 MHz instrument (inset shows the splitting signals at 8.46
ppm of the protons on perylene ring because of the presence of cis and trans
isomers).
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Figure S7. 13C NMR spectrum of 2 in chloroform-d1
Reference
1. Würthner, F.; Thalacker, C.; Diele, S.; Tschierske, C. Chem. Eur. J. 2001, 7,
2245-2253.
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3. Simulated absorption spectra of 3 and 4
Figure S8. Simulated absorption spectra of 3 with different structures based on
TD-DFT calculation.
Figure S9. Simulated absorption spectra of 4 with different structures based on
TD-DFT calculation.
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4. Simulated absorption spectra of 1 and 2.
Figure S10. Simulated absorption spectrum of 1 (solid) compared with the
experimental recorded spectrum (dash).
Figure S11. Simulated absorption spectra of 2 (cis and trans isomer) (solid)
compared with the experimental recorded spectra (dash).
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5. Calculated energy levels and the orbital maps of 1 and 2.
Figure S12. The frontier orbital energy levels and orbital maps of 1.
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Figure S13. The frontier orbital energy levels and orbital maps of cis (left) and trans
(right) isomer of 2.
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