10.1002/chem.201900536
Chemistry - A European Journal
FULL PAPER
145.3, 139.5, 137.4, 134.3, 133.0, 131.6, 119.3. 11B NMR (128 MHz,
CDCl3): δ = 0.20 (t, JB-F = 28.6Hz). 19F NMR (376 MHz, CDCl3): δ = -145.1
(q, JF-B=28.4Hz). HRMS (ESI-TOF): calcd for C22H14B2F4N4S
[M+K]+,503.0701; found 503.0734.
efficient light harvesting behavior, displaying
approximately 1200nm.
a cut-off at
Simultaneously, this dimer exhibits a slightly higher electron
affinity, really close to the fullerene derivatives ones, without
losing its ambipolar feature. Finally, although moderate, the
electron charge carrier mobilities are in the same range in all
directions i.e. the dimer 7 presents isotropic charge-carrier
transport properties. All those desirable features make this class
of polycyclic BODIPY-dimer attractive and promising organic
semiconducting materials for optoelectronic applications.
Synthesis of compound 5. To a stirred solution of compound 4 (145mg,
0.312mmol, 1.0eq) in CHCl3 (30mL) is added at R.T. Br2 (0.48mL, 1.50g,
9.37mmol, 30 eq). The mixture is stirred 3h at R.T. EtOH (15mL) is added,
and the mixture is stirred 15min at R.T. The solid is collected by filtration
and washed with a mixture of CHCl3 and EtOH (7:3, 20mL) to afford pure
compound 5 (200mg, 0.182mmol, 58%) as a red solid. The extreme
insolubility of the product in common organic solvents only allowed HRMS
analysis. HRMS (ESI-TOF): calcd for C22H6B2Br8F4N4S [M+K]+,1134.3463;
found 1134.3463.
Experimental Section
Synthesis of compound 6.
A solution of compound 5 (124.1mg,
Synthesis of compound 1. To a stirred solution of thiophosgene (2.10g,
18.3mmol, 1.0eq) in anhydrous toluene (50mL) is added via cannula and
at 0°C a solution pyrrole (2.45g, 36.5mmol, 2.0eq.) in anhydrous diethyl
ether (25mL). The mixture was stirred at 0°C for 10 minutes before a
mixture of MeOH/H2O (4:1, 100 mL) is added. The mixture is further stirred
at room temperature for 45min. The reaction mixture is evaporated to
dryness under vacuum. Column chromatography on alumina
(PhMe/CHCl3 9:1) afforded 1.86g (10.6mmol, 58%) of pure compound 1
as an orange solid. 1H NMR (400 MHz, CDCl3): δ = 9.77 (b, 2H), 7.21 (s,
2H), 7.05 (s, 2H), 4.40-6.42 (m, 2H). 13C NMR (100 MHz, CDCl3): δ =
193.4, 138.5, 127.8, 114.9, 112.6.
0.113mmol) and tributyl(5-hexylthiophen-2-yl)stannane (1.81 mmol, 16 eq)
in anhydrous toluene is degassed with Argon. Pd(PPh3)4 (13mg,
0.0113mmol, 10mol%) is added and the reaction mixture is stirred at
110°C for 16h. The solvent is removed by vacuum distillation. The resulting
crude product is purified by column chromatography (PE/DCM 4/1).
Trituration in EtOH (20 mL) afforded 104mg of the pure expected product
6 (0.0579mmol, 51%). 1H NMR (400 MHz, C6D6): δ = 7.93 (d, 4H,
3J=3.7Hz), 7.28 (s, 4H), 7.04 (s, 2H), 6.83 (d, 4H, 3J=3.5Hz), 6.59 (d, 4H,
3
3J=3.7Hz), 6.56 (d, 4H, J=3.5Hz), 2.57 (t, 8H, 3J=7.6Hz), 2.45 (t, 8H,
3J=7.6Hz), 1.41 (t, 8H, 3J=7.5Hz), 1.09-1.21 (m, 48H), 0.87 (t, 12H,
3J=7.2Hz), 0.83 (t, 12H, 3J=7.3Hz). 13C NMR (100 MHz, CDCl3): δ = 151.5,
149.8, 146.8, 139.3, 134.5, 132.9, 132.9, 132.7, 132.3, 128.6, 127.2, 127.2,
126.5, 124.8, 124.4, 34.3, 31.7, 31.7, 31.5, 30.4, 30.3, 28.9, 22.7, 22.7,
Synthesis of compound 2. To a stirred solution of dipyrromethanethione
(900mg, 5.11mmol) in MeOH/H20 (28.5/1.5mL) are successively added,
at 0°C, KOH (1.13g) and H202 (30% in water, 3.8mL). After the addition is
over, the mixture is heated at reflux (80°C) for 10 minutes. The solution
turns from deep red to light yellow. After cooling down at room temperature,
water (20mL) is added. The solid is collected by filtration and washed with
water to afford 545mg (3.40mmol, 66%) of the pure dipyrromethanone as
a light yellow solid. 1H NMR (400 MHz, CDCl3): δ = 9.66 (b, 2H), 7.15-7.17
(m, 2H), 7.08-7.09 (m, 2H), 6.35-6.37 (m, 2H). 13C NMR (100 MHz, CDCl3):
δ = 172.8, 130.6, 124.0, 116.0, 111.2.
22.5, 14.2, 14.2. 11B NMR (128 MHz, C6D6): δ = 1.74 (t, JB-F = 30.7Hz). 19
NMR (376 MHz, C6D6): δ = -134.1 (q, JF-B=30.7Hz). HRMS (ESI-TOF):
calcd for C102H126B2F4N4S9 [M]+,1793.7627; found 1793.7695.
F
Synthesis of compound 7. To a stirred solution of compound 8 (73.7mg,
0.0411mmol, 1.0eq) in anhydrous DCM (100mL) is added at 0°C
anhydrous FeCl3 (106mg, 0.657mmol, 16eq). The mixture turns quickly
from black to blue. The reaction mixture is stirred at 0°C for 25min. Water
(50mL) is added. The organic layer is washed twice with water, dried over
MgSO4, filtered off and concentrated under vacuum. Column
chromatography (Cyclohexane/DCM 3:2) followed by recrystallization from
DCM/EtOH afforded the pure expected product 7 (41.1mg, 0.0230mmol,
Synthesis of compound 3. To a solution of dipyrromethanone (217mg,
1.35mmol), in anhydrous DCE (7.0mL) is added dropwise POCl3 (415mg,
0.25mL, 2.0eq). The reaction mixture is heated to reflux for 3h. After
cooling down to 0°C, TEA (1.37g, 1.9mL, 10eq) and BF3.OEt2 (2.11g,
1.9mL, 11eq) are successively added. The mixture is stirred 1h30 at R.T.
before being poured on water and diluted with Et2O. The organic layer is
washed with water. The aqueous layer is extracted with Et2O, dried over
MgSO4, and evaporated to dryness. Column chromatography on silica gel
(DCM/PE 3:2) afforded 173mg (0.764mmol, 56%) of pure compound 3 as
a red solid. 1H NMR (400 MHz, CDCl3): δ = 7.89 (bs, 2H), 7.41 (d, 2H,
3J=4.3Hz), 6.58 (d, 2H, 3J=4.3Hz). 13C NMR (100 MHz, CDCl3): δ = 145.2,
141.3, 134.1, 129.4, 119.2. 11B NMR (128 MHz, CDCl3): δ = 0.08 (t, JB-F
=28.7Hz). 19F NMR (376 MHz, CDCl3): δ = -145.6 (q, JF-B=28.7Hz).
1
56%) as a blue powder. H NMR (400 MHz, C2D2Cl4, 369K): δ = 7.84 (s,
2H), 7.63 (s, 4H), 7.38 (s, 4H), 7.30 (s, 4H), 3.13 (t, 8H, 3J=7.5Hz), 3.00 (t,
8H, 3J=7.4Hz), 1.98 (t, 8H, 3J=7.6Hz), 1.85 (t, 8H, 3J=7.4Hz), 1.56-1.65 (m,
8H), 1.47-1.55 (m, 24H), 1.38-1.44 (m, 16H), 1.02 (t, 12H, 3J=7.2Hz), 0.96
(t, 12H, 3J=7.2Hz). 13C NMR (100 MHz, CDCl3): δ = 154.4, 145.3, 144.8,
139.9, 139.3, 137.1, 131.8, 131.4, 128.2, 126.0, 121.2, 119.8, 119.7, 119.3,
119.1, 30.7, 30.6, 30.4, 30.2, 30.0, 29.7, 28.1, 27.9, 21.7, 21.6. 11B NMR
(128 MHz, CDCl3): δ = 0.87 (t, JB-F = 32.5Hz). 19F NMR (376 MHz, CDCl3):
δ
= -141.0 (bs). HRMS (ESI-TOF): calcd for C102H118B2F4N4S9
[M]+,1785.7001; found 1785.6989.
Keywords: α-fused BODIPY, panchromatic absorbing materials,
Synthesis of compound 4. A solution of compound 3 (158mg, 0.698mmol,
2.2eq) and 2,5-(trimethylstannane)thiophene (130mg, 0.317mmol,
1.00eq) in dry toluene (5.0 mL) was degassed with argon for 30min.
Pd(PPh3)4 was added (18.4mg, 0.0159mmol, 5.0mol%) and the reaction
mixture was heated at 110°C for 3h. The reaction mixture was diluted with
DCM, washed with water. The aqueous layer was extracted with DCM,
dried over MgSO4, and evaporated to dryness. Column chromatography
(PE/DCM 4:6) followed by recrystallization under reduced pressure from
DCM/EtOH afforded 138mg (0.297mmol, 93%) of compound 4 as a red
solid. 1H NMR (400 MHz, CDCl3): δ = 8.00 (s, 4H), 7.68 (s, 2H), 7.32 (d,
4H, 3J=4.1Hz), 6.64 (d, 4H, 3J=4.1Hz). 13C NMR (100 MHz, CDCl3): δ =
high electron affinity material, BODIPY pairing.
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