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DOI: 10.1055/s-0031-1290364
Synthesis and Characterization of Near-Infrared Emissive BODIPY-Based Conjugated Polymers
Publikationsverlauf
Publikationsdatum:
24. Februar 2012 (online)
Abstract
Three novel BODIPY-based conjugated polymers could be synthesized via palladium-catalyzed Sonogashira coupling reaction. Compared with BODIPY model derivatives, the polymers can emit in the range from deep-red to near-infrared region with emission spectral maxima at λ = 640-660 nm and exhibit moderate fluorescent quantum yield from 0.23 to 0.26. Density functional theory (DFT) calculations are performed on three polymers repeat units, and HOMO and LUMO energy levels of the conjugated polymers are estimated.
Key words
organoboron dye - conjugated polymer - BODIPY - near-infrared
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References and Notes
General Procedure
for Polymerization via Sonogashira Polymerization Reaction
A
20 mL Schlenk flask was charged with monomers, catalyst Pd(PPh3)4,
(CuI), and a magnetic stirrer. A 1:1 mixture of degassed anhyd Et3N
and anhyd toluene solvent was then added to the monomers, and the
reaction temperature was raised to 80 ˚C. The
polymerization was continued for 72 h. Then the solvent was evaporated
under vacuum. The residue was dissolved in CH2Cl2 (100
mL) and washed with H2O (3×). The organic layer
was collected, dried over anhyd Na2SO4, and
filtered. The filtrate was concentrated and added to MeOH to precipitate
the polymer. A dark powder was obtained by filtration, further purified with
MeOH, and then dried under vacuum for 24 h to afford polymers.
P1
BODIPY dye 2 (57
mg, 0.1 mol), monomer 5 (103 mg, 0.1 mmol),
Pd(PPh3)4 (12.0 mg, 0.01 mmol), and CuI (1.9
mg, 0.01mmol) were added to a mixture of toluene (3 mL) and Et3N
(3 mL). The mixture was stirred under N2 atmosphere at
80 ˚C for 72 h, and then the solvent was evaporated
under vacuum. The residue was dissolved in CH2Cl2 (100
mL) and washed with H2O (3×). The organic layer
was collected, dried over anhyd Na2SO4, and
filtered. The filtrate was concentrated and added to MeOH to precipitate
the polymer. A dark powder was obtained by filtration, further washed with
MeOH, and then dried under vacuum for 24 h to afford a yield of
59%. ¹H NMR (300 MHz, CDCl3): δ = 7.71-7.65 (br,
5 H), 7.57-7.42 (br, 6 H), 4.24-4.15 (br 12 H),
3.92-3.84 (br, 12 H), 3.76-3.68 (br, 12 H), 3.52
(br, 6 H), 3.68-3.65 (br, 12 H), 3.52 (br, 6 H), 3.37 (br,
6 H), 3.20 (br, 6 H), 2.70 (br, 6 H), 1.42 (br, 6 H). FT-IR (KBr):
3441, 2923, 2823, 1630, 1529, 1384, 1317, 1261, 1095, 1014, 862,
724, 535 cm-¹.
P2
BODIPY
dye 2 (57 mg, 0.1 mol) and monomer 6 (36 mg, 0.1 mmol) were added to a 5 mL
Schlenk flask. Pd(PPh3)4 (12.0 mg, 0.01 mmol)
and CuI (1.9 mg, 0.01 mmol) were added to a mixture of toluene (3
mL) and Et3N (3 mL). The mixture was stirred under N2 atmosphere
at 80 ˚C for 72 h, and then the solvent was evaporated
under vacuum. The polymeriza-tion was carried out according to the
method for polymer P1. A dark blue powder
was obtained by filtration, further washed with MeOH, and then dried
under vacuum for 24 h to afford a yield of 54%. ¹H
NMR (300 MHz, CDCl3): δ = 7.55-7.51
(br, 5 H), 7.32-7.31 (br, 2 H), 4.17-4.15 (br,
12 H), 3.83-3.80 (br, 12 H), 3.65-3.64 (br, 12
H), 3.52-3.50 (br, 12 H), 3.39-3.40 (br, 18 H),
2.75-2.68 (br, 6 H), 1.55 (br, 6 H). FT-IR (KBr): 3445,
2922, 2853, 1530, 1399, 1315, 1272, 1237, 1182, 1011, 1107, 725,
586 cm-¹.
P3
BODIPY
dye 3 (37 mg, 0.1 mol) and monomer 10 (37 mg, 0.1 mmol) were added to a 5
mL Schlenk flask. Pd(PPh3)4 (12.0 mg, 0.01
mmol) and CuI (1.9 mg, 0.01 mmol) were added to a mixture of toluene
(3 mL) and Et3N (3 mL). The mixture was stirred under
N2 atmosphere at 80 ˚C for 72 h, and
then the solvent was evaporated under vacuum. The polymerization
was carried out according to the method for polymer P1.
A dark blue powder was obtained by filtration, further washed with
MeOH, and then dried under vacuum for 24 h to afford a yield of
62%. ¹H NMR (300 MHz, CDCl3): δ = 7.71-7.70
(br, 2 H), 7.53-7.54 (br, 5 H), 4.05-4.02 (br,
4 H), 2.70-2.65 (br, 12 H), 2.05 (br, 3 H), 1.55-1.65 (br,
15 H), 1.28-1.27 (br, 6 H). FT-IR (KBr): 3438, 2924, 2363,
1637, 1527, 1384, 1315, 1261, 1097, 804 cm-¹.