Conjugated BODIPY DYEmers by metathesis reactions

Article abstract of DOI:10.1002/chem.201303468

Boron dipyrrin (BODIPY) DYEmers bridged by conjugating ethynylene and ethenylene moieties can be prepared through metal-promoted metathesis reactions. Alkyne metathesis was advantageous over alkene metathesis and Stille coupling for BODIPY substrates, but also showed specific restrictions with respect to steric encumbrance and regioselectivity. All derivatives with unhindered rotations along the bridges reside in a coplanar minimum conformation. For a hindered β-ethenylene-bridged DYEmer, the shifts in the ¹HNMR spectrum indicate a significant loss of coplanarity and conjugation. The electronic interactions of the BODIPY subchromophores, visualized by optical spectra and cyclic voltammograms, deviate significantly from those found for nonconjugated and excitonically coupled DYEmers. The observed properties can be rationalized in each case by the respective strength of conjugation through the α or β position, the degree of coplanarity, and conformational dynamics. Metal-promoted metathesis is a valuable tool for the efficient syntheses of conjugated di- and oligochromophoric boron dipyrrin (BODIPY) systems (see figure). The BODIPY DYEmers prepared display interesting photophysical properties and show promise in current optoelectronic research.

Full text of DOI:10.1002/chem.201303468

Supporting Information
ꢀ Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014
Conjugated BODIPY DYEmers by Metathesis Reactions**
Johannes Ahrens, Birte Haberlag, Anne Scheja, Matthias Tamm, and Martin Brçring*[a]
chem_201303468_sm_miscellaneous_information.pdf

Conjugated BODIPY DYEmers by Metathesis Reactions
Johannes Ahrens, Birte Haberlag, Anne Scheja, Matthias Tamm and Martin Bröring*
Supporting Information (SI)
A – Preparation and analytical data of BODIPYs 1–8, 15, 21–23, S2, S3, S5, and S8
B – NMR spectra (1H, 13C, 11B, 19F) of BODIPYs and DYEmers 1–8, 10–12, 15–26, S2, S3, S5, and S8
C – Optical spectra of DYEmers 11 and 17.
D – Cyclic voltammogram of DYEmer 10.
A – Preparation and analytical data of BODIPYs 1–8, 15, 21–23, S2, S3, S5, and S8
8-Ethyl-1,3,5,7-tetramethyl-2-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (1)
a) 8-Ethyl-2-iodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (S2): A suspension of BODIPY
S1[SI1] (854 mg, 3.09 mmol) in EtOH (250 mL) and dichloromethane (9 mL) was treated with I2 (471 mg,
1.86 mmol) and the mixture stirred until the iodine was dissolved. HIO3 (164 mg, 0.927 mmol) in H2O (1 mL) was
slowly added. The mixture was heated to 65 °C for 2 h and diluted with dichloromethane (350 mL) after cooling to
ambient temperature. After washing with saturated sodium thiosulfate solution and drying with sodium sulfate all
volatiles were removed in vacuo. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the monoiodo derivative
1
S2 in the second, orange band (547 mg, 1.36 mmol, 44%) as a red solid. H NMR (400 MHz, CDCl3):  = 6.12 (s,
1H; 6-CH), 3.02 (q, J = 7.5 Hz, 2H; CH2CH3), 2.60 (s, 3H; 3-CCH3), 2.53 (s, 3H; 5-CCH3), 2.48 (s, 3H; 1-CCH3),
2.45 (s, 3H; 7-CCH3), 1.31 ppm (t, J = 7.5 Hz, 3H; CH2CH3). 13C NMR (100 MHz, CDCl3):  = 156.3 (1C; 5-CCH3),
153.3 (1C; 3-CCH3), 147.8 (1C; 8-CCH2), 142.5 (1C; 7-CCH3), 140.2 (1C; 1-CCH3), 131.8 (1C; 7a-C), 130.8 (1C;
8a-C), 122.8 (1C; 6-CH), 85.0 (1C; 2-CI), 21.8 (1C; CH2CH3), 18.6 (1C; 1-CCH3), 16.7 (1C; 7-CCH3), 16.0 (t,
TS
TS
J
= 2 Hz, 1C; 3-CCH3), 15.5 (1C; CH2CH3), 14.8 ppm (t,
J
= 2 Hz, 1C; 5-CCH3). 19F NMR (376 MHz,
CF
CF
CDCl3):  = −146.6 (q, JBF = 32 Hz, 1F; BFF), −146.7 ppm (q, JBF = 32 Hz, 1F; BFF). 11B NMR (128 MHz, CDCl3):
 = 0.67 ppm (t, JBF = 32 Hz, 1B; BF2). MS (ESI): m/z = 402 (M+), 383 ([M−F]+). HRMS (ESI): m/z calcd for
C15H18BF2IN2 (M+): 402.0570; found: 402.0574. UV/Vis (CH2Cl2): abs ([rel]) = 368 (0.08), 512.0 nm (1);

em (ex = 512 nm) = 542 nm.
b) 8-Ethyl-1,3,5,7-tetramethyl-2-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (1):
A
solution of
BODIPY S2 (212 mg, 0.527 mmol) in dry toluene (20 mL) was treated with Pd(PPh3)4 (30 mg, 0.026 mmol), then
tri-n-butylprop-1-ynyltin (225 L, 0.738 mmol), and heated with stirring to 95 °C for 2 h. After cooling the mixture
was poured into dichloromethane (30 mL), washed with aqueous KF solution (20 mL, 10%) and water (20 mL), and
dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the propynyl derivative 1 in the
major, orange band (136 mg, 0.432 mmol, 82%) as a red solid. 1H NMR (400 MHz, CDCl3):  = 6.07 (s, 1H; 6-CH),
3.01 (q, J = 7.5 Hz, 2H; CH2CH3), 2.58 (s, 3H; 3-CCH3), 2.52 (s, 3H; 5-CCH3), 2.49 (s, 3H; 1-CCH3), 2.44 (s, 3H;
7-CCH3), 2.12 (s, 3H; CCCH3), 1.30 ppm (t, J = 7.5 Hz, 3H; CH2CH3). 13C NMR (100 MHz, CDCl3):  = 155.6 (1C;
1

3-CCH3), 155.2 (1C; 5-CCH3), 148.2 (1C; 8-CCH2), 141.3 (1C; 7-CCH3), 140.1 (1C; 1-CCH3), 132.0 (1C; 7a-C),
130.2 (1C; 8a-C), 122.2 (1C; 6-CH), 116.3 (1C; 2-CCCCH3), 92.2 (1C; CCCH3), 72.1 (1C; 2-CC), 21.6 (1C;
TS
CH2CH3), 16.5 (1C; 1-CCH3), 15.5 (1C; CH2CH3), 14.9 (1C; 7-CCH3), 14.7 (t,
J
= 2 Hz, 1C; 5-CCH3), 13.5 (t,
CF
TS
J
= 2 Hz, 1C; 3-CCH3), 4.8 ppm (1C; CCCH3). 19F NMR (376 MHz, CDCl3):  = −147.2 ppm (q, JBF = 32 Hz,
CF
2F; BF2). 11B NMR (128 MHz, CDCl3):  = 0.67 ppm (t, JBF = 32 Hz, 1B; BF2). MS (ESI): m/z = 337 ([M+Na]+),
315 ([M+H]+), 295 ([M−F]+). HRMS (ESI): m/z calcd for C18H22BF2N2 ([M+H]+): 315.1839; found: 315.1840.
UV/Vis (CH2Cl2): abs ([rel]) = 382 (0.12), 525 nm (1); em (ex = 500 nm) = 545 nm.
8-Ethyl-2-iodo-1,3,5,7-tetramethyl-6-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (2)
a) 8-Ethyl-2,6-diiodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (S3): A suspension of BODIPY
S1[SI1] (811 mg, 2.94 mmol) in EtOH (150 mL) and CH2Cl2 (9 mL) was treated with I2 (596 mg, 2.35 mmol) and the
mixture stirred until the iodine was dissolved. HIO3 (413 mg, 2.35 mmol) in H2O (0.5 mL) was slowly added. The
mixture was heated to 65 °C for 1 h and diluted with dichloromethane (200 mL) after cooling to ambient temperature.
After washing with saturated sodium thiosulfate solution and drying with sodium sulfate all volatiles were removed
in vacuo. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the monoiodo derivative S2 in the major, violet-red
1
band (1.46 g, 2.77 mmol, 94%) as a red solid. H NMR (400 MHz, CDCl3):  = 3.07 (q, J = 7.6 Hz, 2H; CH2CH3),
2.62 (s, 6H; 3/5-CCH3), 2.50 (s, 6H; 1/7-CCH3), 1.32 ppm (t, J = 7.6 Hz, 3H; CH2CH3). 13C NMR (100 MHz,
CDCl3):  = 155.5 (2C; 3/5-CCH3), 147.7 (1C; 8-CCH2), 142.4 (2C; 1/7-CCH3), 131.8 (2C; 7a/8a-C), 86.5 (2C; 2/6-
TS
CI), 22.3 (1C; CH2CH3), 19.0 (2C; 1/7-CCH3), 16.0 (t,
J
= 3 Hz, 2C; 3/5-CCH3), 15.4 ppm (1C; CH2CH3). 19F
CF
NMR (376 MHz, CDCl3):  = −146.2 (q, JBF = 32 Hz, 1F; BFF), −146.3 ppm (q, JBF = 32 Hz, 1F; BFF). 11B NMR
(128 MHz, CDCl3):  = 0.57 ppm (t, JBF = 32 Hz, 1B; BF2). MS (ESI): m/z = 551 ([M+Na]+), 528 (M+), 509 ([M−F]+).
HRMS (ESI): m/z calcd for C15H17BF2I2N2 (M+): 527.9537; found: 527.9530. UV/Vis (CH2Cl2): abs ([rel]) = 379
(0.10), 530 nm (1); em (ex = 500 nm) = 550 nm.
b) 8-Ethyl-2-iodo-1,3,5,7-tetramethyl-6-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (2): A solution of
BODIPY S3 (437 mg, 0.829 mmol) in dry toluene (20 mL) was treated with Pd(PPh3)4 (29 mg, 0.025 mmol), then
tri-n-butylprop-1-ynyltin (265 L, 0.870 mmol), and heated with stirring to 95 °C for 3.5 h. After cooling the
mixture was poured into dichloromethane (30 mL), washed with aqueous KF solution (20 mL, 10%) and water
(20 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:3) yielded the propynyl
derivative 2 in the second, orange band (116 mg, 0.264 mmol, 32%) as a red solid. 1H NMR (400 MHz, CDCl3):  =
3.05 (q, J = 7.5 Hz, 2H; CH2CH3), 2.60 (s, 3H; 3-CCH3), 2.59 (s, 3H; 5-CCH3), 2.51 (s, 3H; 7-CCH3), 2.49 (s, 3H; 1-
CCH3), 2.12 (s, 3H; CCCH3), 1.31 ppm (t, J = 7.5 Hz, 3H; CH2CH3). 13C NMR (100 MHz, CDCl3):  = 157.8 (1C;
5-CCH3), 154.4 (1C; 3-CCH3), 148.0 (1C; 8-CCH2), 142.1 (1C; 7-CCH3), 141.1 (1C; 1-CCH3), 131.5 (1C; 8a-C),
130.7 (1C; 7a-C), 117.7 (1C; 6-CCCCH3), 93.1 (1C; CCCH3), 85.7 (1C; 2-CI), 71.7 (1C; 6-CC), 22.0 (1C; CH2CH3),
TS
18.8 (1C; 1-CCH3), 16.1 (t,
J
= 3 Hz, 1C; 3-CCH3), 15.4 (1C; CH2CH3), 15.2 (1C; 7-CCH3), 13.7 (br s, 1C; 5-
CF
CCH3), 4.8 ppm (1C; CCCH3). 19F NMR (376 MHz, CDCl3):  = −146.8 (q, JBF = 32 Hz, 1F; BFF), −146.8 ppm (q,
JBF = 32 Hz, 1F; BFF). 11B NMR (128 MHz, CDCl3):  = 0.56 ppm (t, JBF = 32 Hz, 1B; BF2). MS (ESI): m/z = 903
2

([2M+Na]+), 463 ([M+Na]+), 441 ([M+H]+), 421 ([M−F]+). HRMS (ESI): m/z calcd for C18H21BF2IN2 ([M+H]+):
441.0805; found: 441.0804. UV/Vis (CH2Cl2): abs ([rel]) = 385 (0.13), 542 nm (1); em (ex = 500 nm) = 561 nm.
8-Ethyl-1,3,5,7-tetramethyl-2,6-di-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (3)
A solution of BODIPY S3 (290 mg, 0.549 mmol) in dry toluene (20 mL) was treated with Pd(PPh3)4 (32 mg,
0.027 mmol), then tri-n-butylprop-1-ynyltin (500 L, 1.65 mmol), and heated with stirring to 95 °C for 5 h. After
cooling the mixture was poured into dichloromethane (30 mL), washed with aqueous KF solution (20 mL, 10%) and
water (20 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:3) yielded the propynyl
1
derivative 3 in the major orange band (149 mg, 0.423 mmol, 77%) as a red solid. H NMR (400 MHz, CDCl3):  =
3.03 (q, J = 7.5 Hz, 4H; 2×CH2CH3), 2.58 (s, 6H; 3/5-CCH3), 2.49 (s, 6H; 1/7-CCH3), 2.12 (s, 6H; 2×CCCH3),
1.30 ppm (t, J = 7.5 Hz, 6H; 2×CH2CH3). 13C NMR (100 MHz, CDCl3):  = 156.7 (2C; 3/5-CCH3), 148.3 (1C; 8-
CCH2), 140.9 (2C; 1/7-CCH3), 130.8 (2C; 7a/8a-C), 117.0 (2C; 2/6-CC), 92.6 (2C; 2×CCCH3), 72.9 (2C; 2/6-CC),
TS
21.7 (1C; CH2CH3), 15.5 (1C; CH2CH3), 15.0 (2C; 1/7-CCH3), 13.6 (t,
J
= 2 Hz, 2C; 3/5-CCH3), 4.8 ppm (2C;
CF
2×CCCH3). 19F NMR (376 MHz, CDCl3):  = −147.3 ppm (q, JBF = 32 Hz, 2F; BF2). 11B NMR (128 MHz, CDCl3):
 = 0.56 ppm (t, JBF = 32 Hz, 1B; BF2). MS (ESI): m/z = 1080 ([3M+Na]+), 727 ([2M+Na]+), 375 ([M+Na]+), 353
([M+H]+), 333 ([M−F]+). HRMS (ESI): m/z calcd for C21H24BF2N2 ([M+H]+): 353.1995; found: 353.1992. UV/Vis
(CH2Cl2): abs ([rel]) = 389 (0.14), 552 nm (1); em (ex = 555 nm) = 573 nm.
2-Iodo-8-mesityl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (4)
a) 2-Iodo-8-mesityl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (S5): A solution of BODIPY
S4[SI2] (768 mg, 2.10 mmol) in EtOH (150 mL) was treated with I2 (234 mg, 0.923 mmol) and the mixture stirred
until the iodine was dissolved. HIO3 (81 mg, 0.461 mmol) in H2O (2 mL) was slowly added. The mixture was heated
to 65 °C for 1 h and diluted with dichloromethane (300 mL) after cooling to ambient temperature. After washing
with saturated sodium thiosulfate solution and drying with sodium sulfate all volatiles were removed in vacuo.
Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the monoiodo derivative S5 in the second, orange band
(773 mg, 1.57 mmol, 75%) as a red solid. 1H NMR (400 MHz, CDCl3):  = 6.96 (s, 2H; 2×mesityl-CH), 6.03 (s, 1H;
6-CH), 2.63 (s, 3H; 3-CCH3), 2.57 (s, 3H; 5-CCH3), 2.34 (s, 3H; mesityl-para-CH3), 2.07 (s, 6H; 2×mesityl-ortho-
CH3), 1.40 (s, 3H; 1-CCH3), 1.38 ppm (s, 3H; 7-CCH3). 13C NMR (100 MHz, CDCl3):  = 157.6 (1C; 5-CCH3),
154.2 (1C; 3-CCH3), 144.5 (1C; 7-CCH3), 142.5 (1C; 1-CCH3), 141.8 (1C; 8-C), 139.1 (1C; mesityl-para-CCH3),
135.0 (2C; 2×mesityl-ortho-CCH3), 131.3 (1C; 7a-C), 131.1 (1C; mesityl-C), 130.2 (1C; 8a-C), 129.3 (2C;
3

2×mesityl-CH), 122.0 (1C; 6-CH), 84.0 (1C; 2-CI), 21.4 (1C; mesityl-para-CH3), 19.6 (2C; 2×mesityl-ortho-CH3),
15.9 (br s, 1C; 3-CCH3), 15.6 (1C; 1-CCH3), 14.9 (br s, 1C; 5-CCH3), 13.8 ppm (1C; 7-CCH3). 19F NMR (376 MHz,
CDCl3):  = −146.5 ppm (q, JBF = 33 Hz, 2F; BF2). 11B NMR (128 MHz, CDCl3):  = 0.90 ppm (t, JBF = 33 Hz, 1B;
BF2). MS (ESI): m/z = 1007 ([2M+Na]+), 515 ([M+Na]+), 493 ([M+H]+), 473 ([M−F]+). HRMS (ESI): m/z calcd for
C22H25BF2IN2 ([M+H]+): 493.1118; found: 493.1110. UV/Vis (CH2Cl2): abs ([rel]) = 372 (0.09), 516 nm (1);

em (ex = 516 nm) = 535 nm.
b) 2-Iodo-8-mesityl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (4): A solution of BODIPY S5
(628 mg, 1.276 mmol) in dry toluene (25 mL) was treated with Pd(PPh3)4 (74 mg, 0.064 mmol), then tri-n-butylprop-
1-ynyltin (0.58 mL, 1.914 mmol), and heated with stirring to 95 °C for 4 h. After cooling the mixture was poured
into dichloromethane (50 mL), washed with aqueous KF solution (2×20 mL, 10%) and water (20 mL), and dried
with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the propynyl derivative 4 in the major,
orange-red band (485 mg, 1.20 mmol, 94%) as a red solid. 1H NMR (400 MHz, CDCl3):  = 6.95 (s, 2H; 2×mesityl-
CH), 5.98 (s, 1H; 6-CH), 2.61 (s, 3H; 3-CCH3), 2.56 (s, 3H; 5-CCH3), 2.34 (s, 3H; mesityl-para-CH3), 2.07 (s, 6H;
2×mesityl-ortho-CH3), 2.06 (s, 3H; CCCH3), 1.43 (s, 3H; 1-CCH3), 1.38 ppm (s, 3H; 7-CCH3). 13C NMR (100 MHz,
CDCl3):  = 156.8 (1C; 3-CCH3), 156.5 (1C; 5-CCH3), 143.4 (1C; 7-CCH3), 142.2 (1C; 1-CCH3), 142.1 (1C; 8-C),
138.9 (1C; mesityl-para-CCH3), 135.0 (2C; 2×mesityl-ortho-CCH3), 131.5 (1C; 7a-C), 131.1 (1C; mesityl-C), 129.4
(1C; 8a-C), 129.2 (2C; 2×mesityl-CH), 121.4 (1C; 6-CH), 115.8 (1C; 2-CC), 92.1 (1C; CCCH3), 71.9 (1C; 2-CC),
21.4 (1C; mesityl-para-CH3), 19.6 (2C; 2×mesityl-ortho-CH3), 14.8 (br s, 1C; 5-CCH3), 13.6 (1C; 7-CCH3), 13.6 (br
s, 1C; 3-CCH3), 12.2 (1C; 1-CCH3), 4.7 ppm (1C; CCCH3). 19F NMR (376 MHz, CDCl3):  = −147.0 ppm (q, JBF
=
33 Hz, 2F; BF2). 11B NMR (128 MHz, CDCl3):  = 0.89 ppm (t, JBF = 33 Hz, 1B; BF2). MS (ESI): m/z = 831
([2M+Na]+), 427 ([M+Na]+), 405 ([M+H]+), 385 ([M−F]+). HRMS (ESI): m/z calcd for C25H28BF2N2 ([M+H]+):
405.2308; found: 405.2307. UV/Vis (CH2Cl2): abs ([rel]) = 384 (0.12), 530 nm (1) ; em (ex = 450 nm) = 553 nm.
8-Mesityl-1,3,5,7-tetramethyl-2,6-di-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (5)
A solution of BODIPY S6[SI3] (590 mg, 0.955 mmol) in dry toluene (20 mL) was treated with Pd(PPh3)4 (83 mg,
0.072 mmol), then tri-n-butylprop-1-ynyltin (0.94 mL, 3.10 mmol), and heated with stirring to 95 °C for 4 h. After
cooling the mixture was poured into dichloromethane (200 mL), washed with aqueous KF solution (30 mL, 10%)
and water (30 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the
1
propynyl derivative 5 in the major orange band (419 mg, 0.947 mmol, 99%) as a red solid. H NMR (400 MHz,
CDCl3):  = 6.95 (s, 2H; 2×mesityl-CH), 2.61 (s, 6H; 3/5-CCH3), 2.35 (s, 3H; mesityl-para-CH3), 2.06 (s, 6H;
2×CCCH3), 2.05 (s, 6H; 2×mesityl-ortho-CH3), 1.42 ppm (s, 6H; 1/7-CCH3). 13C NMR (100 MHz, CDCl3):  =
157.9 (2C; 3/5-CCH3), 143.0 (2C; 1/7-CCH3), 142.3 (1C; 8-C), 139.0 (1C; mesityl-para-CCH3), 135.0 (2C;
2×mesityl-ortho-CCH3), 130.9 (1C; mesityl-C), 130.1 (2C; 7a/8a-C), 129.2 (2C; 2×mesityl-CH), 116.4 (2C; 2/6-C),
92.5 (2C; 2×CCCH3), 71.7 (2C; 2/6-CC), 21.4 (1C; mesityl-para-CH3), 19.6 (2C; 2×mesityl-ortho-CH3), 13.7 (br s,
2C; 3/5-CCH3), 12.3 (2C; 1/7-CCH3), 4.8 ppm (2C; 2×CCCH3). 19F NMR (376 MHz, CDCl3):  = −147.2 ppm (q,
4

JBF = 32 Hz, 2F; BF2). 11B NMR (128 MHz, CDCl3):  = 0.77 ppm (t, JBF = 32 Hz, 1B; BF2). MS (ESI): m/z = 465
([M+Na]+), 443 ([M+H]+), 423 ([M−F]+). HRMS (ESI): m/z calcd for C28H30BF2N2 ([M+H]+): 443.2465; found:
443.2461. UV/Vis (CH2Cl2): abs ([rel]) = 396 (0.16), 557 nm (1); em (ex = 555 nm) = 579 nm.
3-Bromo-8-mesityl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (15) and 3,5-dibromo-8-mesityl-4,4-difluoro-4-
bora-3a,4a-diaza-s-indacene (S8)
A solution of 5-mesityldipyrromethane[SI4] (670 mg, 2.53 mmol) in dry THF (60 mL) was treated under nitrogen at
−78 °C with N-bromosuccinimide (450 mg, 2.53 mmol), stirred for 1 h and allowed to warm to ambient temperature.
A solution of DDQ (574 mg, 2.53 mmol) in THF (10 mL) was added within 10 min. The solvent was removed in
vacuo and the residue was redissolved in CH2Cl2 and filtered over silica. After drying in vacuo, the oily brownish
residue was dissolved in dry CH2Cl2 (120 mL) and treated successively with iPr2EtN (12.9 mL, 76 mmol) and
BF3 ·OEt2 (14 mL, 114 mmol). The mixture was stirred for 1.5 h, washed with saturated sodium carbonate solution
(3×100 mL) and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the dibrominated
product S8 in a first, orange-red fraction (red solid, 154 mg, 0.329 mmol, 13%), and the monobrominated product 15
in a second, yellow-orange band (red solid, 270 mg, 0.694 mmol, 27%).
1
3-Bromo-8-mesityl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (15): H NMR (400 MHz, CDCl3):  = 7.93 (s, 1H;
5-CH), 6.95 (s, 2H; 2×mesityl-CH), 6.68 (d, J = 4.2 Hz, 1H; 7-CH), 6.56 (d, J = 4.2 Hz, 1H; 1-CH), 6.49 (m, J =
4.2 Hz, 1H; 6-CH), 6.44 (d, J = 4.2 Hz, 1H; 2-CH), 2.36 (s, 3H; mesityl-para-CH3), 2.09 ppm (s, 6H; 2×mesityl-
ortho-CH3). 13C NMR (100 MHz, CDCl3):  = 145.7 (1C; 8-C), 145.1 (1C; 5-CH), 139.2 (1C; mesityl-para-CCH3),
136.6 (2C; 2×mesityl-ortho-CCH3), 136.1 (1C; 8a-C), 135.4 (1C; 7a-C), 131.8 (1C; 3-CBr), 130.4 (2C; 1-CH and 7-
CH), 129.1 (1C; mesityl-C), 128.4 (2C; 2×mesityl-CH), 122.2 (1C; 2-CH), 119.3 (1C; 6-CH), 21.3 (1C; mesityl-
para-CH3), 20.1 ppm (2C; 2×mesityl-ortho-CH3). 19F NMR (376 MHz, CDCl3):  = −147.4 ppm (q, JBF = 29 Hz, 2F;
BF2). 11B NMR (128 MHz, CDCl3):  = 0.68 ppm (t, JBF = 29 Hz, 1B; BF2). MS (ESI): m/z = 817 ([2M+K]+), 801
([2M+Na]+), 427 ([M+K]+), 411 ([M+Na]+), 389 ([M+H]+), 369 ([M−F]+). HRMS (ESI): m/z calcd for
C18H16BBrF2N2Na ([M+Na]+): 411.0450; found: 411.0455. UV/Vis (CH2Cl2): abs ([rel]) = 359 (0.08), 511 nm (1);

em (ex = 511 nm) = 525 nm.
1
3,5-Dibromo-8-mesityl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (S8): H NMR (400 MHz, CDCl3):  = 6.94 (s,
2H; 2×mesityl-CH), 6.55 (d, J = 4.2 Hz, 2H; 1/7-CH), 6.46 (d, J = 4.2 Hz, 2H; 2/6-CH), 2.35 (s, 3H; mesityl-para-
CH3), 2.09 ppm (s, 6H; 2×mesityl-ortho-CH3). 13C NMR (100 MHz, CDCl3):  = 143.4 (1C; 8-C), 139.4 (1C;
mesityl-para-CCH3), 136.7 (2C; 2×mesityl-ortho-CCH3), 136.0 (2C; 7a/8a-C), 132.8 (2C; 3/5-CBr), 130.5 (2C; 1/7-
CH), 128.4 (2C; 2×mesityl-CH), 128.4 (1C; mesityl-C), 122.9 (2C; 2/6-CH), 21.3 (1C; mesityl-para-CH3), 20.1 ppm
(2C; 2×mesityl-ortho-CH3). 19F NMR (376 MHz, CDCl3):  = −147.7 ppm (q, JBF = 28 Hz, 2F; BF2). 11B NMR
(128 MHz, CDCl3):  = 0.89 ppm (t, JBF = 28 Hz, 1B; BF2). MS (ESI): m/z = 975 ([2M+K]+), 959 ([2M+Na]+), 507
([M+K]+), 491 ([M+Na]+), 469 ([M+H]+), 449 ([M−F]+). HRMS (ESI): m/z calcd for C18H15BBr2F2N2Na ([M+Na]+):
5

490.9540; found: 490.9537. UV/Vis (CH2Cl2): abs ([rel]) = 315 (0.09), 495 (0.24), 523 nm (1); em (ex
=
523 nm) = 537 nm.
8-Mesityl-3-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (6)
A solution of BODIPY 15 (215 mg, 0.553 mmol) in dry toluene (10 mL) was treated with Pd(PPh3)4 (48 mg,
0.041 mmol), then tri-n-butylprop-1-ynyltin (252 L, 0.830 mmol), and heated with stirring to 95 °C for 4.5 h. After
cooling the mixture was poured into dichloromethane (30 mL), washed with aqueous KF solution (20 mL, 10%) and
water (20 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the propynyl
derivative 6 in the major orange band (166 mg, 0.477 mmol, 86%) as a violet-red solid. 1H NMR (400 MHz, CDCl3):
 = 7.88 (s, 1H; 5-CH), 6.94 (s, 2H; 2×mesityl-CH), 6.62 (d, 3J = 4.2 Hz, 1H; 7-CH), 6.58 (d, 3J = 4.2 Hz, 1H; 1-CH),
3
3
6.48 (d, J = 4.2 Hz, 1H; 2-CH), 6.46 (m, J = 4.1 Hz, 1H; 6-CH), 2.35 (s, 3H; mesityl-para-CH3), 2.25 (s, 3H;
CCCH3), 2.08 ppm (s, 6H; 2×mesityl-ortho-CH3). 13C NMR (100 MHz, CDCl3):  = 145.1 (1C; 8-C), 144.3 (1C; 5-
CH), 139.2 (1C; 3-CC), 138.9 (1C; mesityl-para-CCH3), 136.6 (2C; 2×mesityl-ortho-CCH3), 135.8 (1C; 8a-C),
135.7 (1C; 7a-C), 129.9 (1C; 1-CH), 129.9 (1C; mesityl-C), 129.5 (1C; 7-CH), 128.3 (2C; 2×mesityl-CH), 123.6
(1C; 2-CH), 118.7 (1C; 6-CH), 100.6 (1C; CCCH3), 73.3 (1C; 3-CC), 21.3 (1C; mesityl-para-CH3), 20.1 (2C;
2×mesityl-ortho-CH3), 5.6 ppm (1C; CCCH3). 19F NMR (376 MHz, CDCl3):  = −147.5 ppm (q, JBF = 29 Hz, 2F;
BF2). 11B NMR (128 MHz, CDCl3):  = 0.63 ppm (t, JBF = 29 Hz, 1B; BF2). MS (ESI): m/z = 371 ([M+Na]+), 349
([M+H]+), 329 ([M−F]+). HRMS (ESI): m/z calcd for C21H20BF2N2 ([M+H]+): 349.1682; found: 349.1682. UV/Vis
(CH2Cl2): abs ([rel]) = 370 (0.07), 504 (0.25), 532 nm (1); em (ex = 500 nm) = 545 nm.
8-Mesityl-3,5-di-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (7)
A solution of BODIPY S8 (63 mg, 0.135 mmol) in dry toluene (10 mL) was treated with Pd(PPh3)4 (16 mg,
0.014 mmol), then tri-n-butylprop-1-ynyltin (103 L, 0.338 mmol), and heated with stirring to 95 °C for 3 h. After
cooling the mixture was poured into dichloromethane (30 mL), washed with aqueous KF solution (20 mL, 10%) and
water (20 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:1) yielded the propynyl
derivative 7 in the major red band (39 mg, 0.100 mmol, 74%) as a red solid. 1H NMR (400 MHz, CDCl3):  = 6.92 (s,
2H; 2×mesityl-CH), 6.52 (d, 3J = 4.2 Hz, 2H; 1/7-CH), 6.47 (d, 3J = 4.2 Hz, 2H; 2/6-CH), 2.34 (s, 3H; mesityl-para-
CH3), 2.24 (s, 6H; 2×CCCH3), 2.07 ppm (s, 6H; 2×mesityl-ortho-CH3). 13C NMR (100 MHz, CDCl3):  = 142.4 (1C;
6

8-C), 139.1 (2C; 3/5-CC), 138.9 (1C; mesityl-para-CCH3), 136.8 (2C; 2×mesityl-ortho-CCH3), 136.1 (2C; 7a/8a-C),
129.9 (1C; mesityl-C), 129.0 (2C; 1/7-CH), 128.3 (2C; 2×mesityl-CH), 123.9 (2C; 2/6-CH), 100.6 (2C; 2×CCCH3),
73.5 (2C; 3/5-CC), 21.3 (1C; mesityl-para-CH3), 20.1 (2C; 2×mesityl-ortho-CH3), 5.7 ppm (2C; 2×CCCH3). 19F
NMR (376 MHz, CDCl3):  = −148.1 ppm (q, JBF = 28 Hz, 2F; BF2). 11B NMR (128 MHz, CDCl3):  = 0.75 ppm (t,
JBF = 28 Hz, 1B; BF2). MS (ESI): m/z = 795 ([2M+Na]+), 409 ([M+Na]+), 387 ([M+H]+), 367 ([M−F]+). HRMS
(ESI): m/z calcd for C24H22BF2N2 ([M+H]+): 387.1839; found: 387.1839. UV/Vis (CH2Cl2): abs ([rel]) = 384 (0.14),
545 (0.75), 564 nm (1); em (ex = 564 nm) = 575 nm.
8-Mesityl-2-(prop-1-ynyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (8)
A solution of BODIPY S9[SI5] (235 mg, 0.604 mmol) in dry toluene (12 mL) was treated with Pd(PPh3)4 (52 mg,
0.045 mmol), then tri-n-butylprop-1-ynyltin (276 L, 0.906 mmol), and heated with stirring to 95 °C for 3 h. After
cooling the mixture was poured into dichloromethane (50 mL), washed with aqueous KF solution (2×20 mL, 10%)
and water (2×20 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:2) yielded the
1
propynyl derivative 8 in the major magenta colored band (165 mg, 0.474 mmol, 78%) as a violet solid. H NMR
3
(400 MHz, CDCl3):  = 7.93 (s, 1H; 5-CH), 7.88 (s, 1H; 3-CH), 6.94 (s, 2H; 2×mesityl-CH), 6.71 (d, J = 4.2 Hz,
1H; 7-CH), 6.62 (s, 1H; 1-CH), 6.48 (m, 1H; 6-CH), 2.35 (s, 3H; mesityl-para-CH3), 2.09 (s, 6H; 2×mesityl-ortho-
CH3), 1.98 ppm (s, 3H; CCCH3). 13C NMR (100 MHz, CDCl3):  = 147.8 (1C; 8-C), 146.0 (1C; 5-CH), 145.3 (1C;
3-CH), 139.1 (1C; mesityl-para-CCH3), 136.4 (2C; 2×mesityl-ortho-CCH3), 136.1 (1C; 7a-C), 134.6 (1C; 8a-C),
130.9 (1C; 7-CH), 130.7 (1C; 1-CH), 129.5 (1C; mesityl-C), 128.3 (2C; 2×mesityl-CH), 119.1 (1C; 6-CH), 115.4
(1C; 2-C), 88.8 (1C; CCCH3), 72.2 (1C; 2-CC), 21.3 (1C; mesityl-para-CH3), 20.1 (2C; 2×mesityl-ortho-CH3),
4.5 ppm (1C; CCCH3). 19F NMR (376 MHz, CDCl3):  = −146.2 ppm (q, JBF = 29 Hz, 2F; BF2). 11B NMR
(128 MHz, CDCl3):  = 0.34 ppm (t, JBF = 29 Hz, 1B; BF2). MS (ESI): m/z = 369 ([M−2H+Na]+), 329 ([M−F]+).
HRMS (ESI): m/z calcd for C21H19BFN2 ([M−F]+): 329.1620; found: 329.1622. UV/Vis (CH2Cl2): abs ([rel]) = 384
(0.23), 540 nm (1); em (ex = 540 nm) = 571 nm.
8-Mesityl-1,3,5,7-tetramethyl-2-vinyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (21)
A solution of BODIPY S5 (460 mg, 0.935 mmol) in dry toluene (15 mL) was treated with Pd(PPh3)4 (54 mg,
0.047 mmol), then tri-n-butylvinyltin (0.55 mL, 1.870 mmol), and heated with stirring at reflux for 5 h. After cooling
7

the mixture was poured into dichloromethane (50 mL), washed with aqueous KF solution (2×50 mL, 10%) and water
(50 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:2, then 1:1) yielded the ethenyl
1
derivative 21 in the major orange-red colored band (308 mg, 0.785 mmol, 84%) as a red solid. H NMR (400 MHz,
CDCl3):  = 6.95 (s, 2H; 2×mesityl-CH), 6.48 (dd, 3Jtrans = 17.9 Hz, 3Jcis = 11.6 Hz, 1H; CHCHH), 5.97 (s, 1H; 6-CH),
3
5.30 (dd, 3Jcis = 11.6 Hz, 2J = 1.6 Hz, 1H; CHCHcisH), 5.28 (dd, Jtrans = 17.9 Hz, 2J = 1.6 Hz, 1H; CHCHHtrans), 2.64
(s, 3H; 3-CCH3), 2.56 (s, 3H; 5-CCH3), 2.34 (s, 3H; mesityl-para-CH3), 2.10 (s, 6H; 2×mesityl-ortho-CH3), 1.42 (s,
3H; 1-CCH3), 1.37 ppm (s, 3H; 7-CCH3). 13C NMR (100 MHz, CDCl3):  = 155.5 (1C; 5-CCH3), 154.3 (1C; 3-
CCH3), 142.6 (1C; 7-CCH3), 141.9 (1C; 8-C), 138.8 (1C; mesityl-para-CCH3), 138.4 (1C; 1-CCH3), 135.2 (2C;
2×mesityl-ortho-CCH3), 131.4 (1C; mesityl-C), 131.0 (1C; 7a-C), 130.1 (1C; 8a-C), 129.2 (2C; 2×mesityl-CH),
128.6 (1C; 2-CCH), 128.1 (1C; CHCHH), 121.2 (1C; 6-CH), 116.7 (1C; CHCHH), 21.4 (1C; mesityl-para-CH3),
19.7 (2C; 2×mesityl-ortho-CH3), 14.8 (br s, 1C; 5-CCH3), 13.9 (br s, 1C; 3-CCH3), 13.6 (1C; 7-CCH3), 11.5 ppm
(1C; 1-CCH3). 19F NMR (376 MHz, CDCl3):  = −146.1 ppm (q, JBF = 33 Hz, 2F; BF2). 11B NMR (128 MHz,
CDCl3):  = 1.04 ppm (t, JBF = 33 Hz, 1B; BF2). MS (ESI): m/z = 807 ([2M+Na]+), 415 ([M+Na]+), 393 ([M+H]+),
373 ([M−F]+). HRMS (ESI): m/z calcd for C24H28BF2N2 ([M+H]+): 393.2308; found: 393.2309. UV/Vis (CH2Cl2):

abs ([rel]) = 388 (0.13), 524 nm (1); em (ex = 520 nm) = 560 nm.
8-Mesityl-1,3,5,7-tetramethyl-2,6-divinyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (22)
A solution of BODIPY S6[SI3] (426 mg, 0.689 mmol) in dry toluene (12 mL) was treated with Pd(PPh3)4 (80 mg,
0.069 mmol), then tri-n-butylvinyltin (0.6 mL, 2.067 mmol), and heated with stirring at reflux for 5 h. After cooling
the mixture was poured into dichloromethane (50 mL), washed with aqueous KF solution (2×25 mL, 10%) and water
(25 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:2, then 1:1) yielded the ethenyl
1
derivative 22 in the major violet-red colored band (175 mg, 0.418 mmol, 61%) as a red solid. H NMR (400 MHz,
3
C6D6):  = 6.69 (s, 2H; 2×mesityl-CH), 6.27 (m, 2H; 2×CHCHH), 5.12 (s, 2H; 2×CHCHHtrans), 5.08 (dd, Jcis
=
2
6.1 Hz, J = 1.6 Hz, 2H; 2×CHCHcisH), 2.71 (s, 6H; 3/5-CCH3), 2.08 (s, 3H; mesityl-para-CH3), 1.94 (s, 6H;
2×mesityl-ortho-CH3), 1.43 ppm (s, 6H; 1/7-CCH3). 13C NMR (100 MHz, C6D6):  = 155.3 (2C; 3/5-CCH3), 142.0
(1C; 8-C), 138.8 (1C; mesityl-para-CCH3), 138.0 (2C; 1/7-CCH3), 135.6 (2C; 2×mesityl-ortho-CCH3), 132.1 (1C;
mesityl-C), 130.7 (2C; 7a/8a-C), 129.4 (2C; 2/6-C), 129.3 (2C; 2×mesityl-CH), 128.2 (2C; 2×CHCHH), 116.9 (2C;
2×CHCHH), 21.1 (1C; mesityl-para-CH3), 19.4 (2C; 2×mesityl-ortho-CH3), 14.1 (br s, 2C; 3/5-CCH3), 11.5 ppm
(2C; 1/7-CCH3). 19F NMR (376 MHz, C6D6):  = −144.0 ppm (q, JBF = 33 Hz, 2F; BF2). 11B NMR (128 MHz, C6D6):
 = 1.68 ppm (t, JBF = 33 Hz, 1B; BF2). MS (ESI): m/z = 419 ([M+H]+), 399 ([M−F]+). HRMS (ESI): m/z calcd for
C26H30BF2N2 ([M+H]+): 419.2465; found: 419.2463. UV/Vis (CH2Cl2): abs ([rel]) = 394 (0.20), 549 nm (1);

em (ex = 549 nm) = 583 nm.
8

8-Mesityl-2-vinyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (23)
A solution of BODIPY S9[SI5] (258 mg, 0.663 mmol) in dry toluene (10 mL) was treated with Pd(PPh3)4 (57 mg,
0.050 mmol), then tri-n-butylvinyltin (0.29 mL, 0.994 mmol), and heated with stirring at 95 °C for 4 h. After cooling
the mixture was poured into dichloromethane (100 mL), washed with aqueous KF solution (3×50 mL, 10%) and
water (50 mL), and dried with sodium sulfate. Chromatography (silica, CH2Cl2/n-pentane 1:2, then 1:1) yielded the
1
ethenyl derivative 23 in the major violet band (170 mg, 0.506 mmol, 76%) as a violet solid. H NMR (400 MHz,
CD2Cl2):  = 8.00 (s, 1H; 3-CH), 7.88 (s, 1H; 5-CH), 6.99 (s, 2H; 2×mesityl-CH), 6.67 (d, J = 4.2 Hz, 1H; 7-CH),
3
6.62 (s, 1H; 1-CH), 6.51 (dd, 3Jtrans = 17.7 Hz, Jcis = 11.0 Hz, 1H; CHCHH), 6.50 (m, 1H; 6-CH), 5.55 (dd, 3Jtrans
=
2
3
2
17.7 Hz, J = 1.1 Hz, 1H; CHCHHtrans), 5.17 (dd, Jcis = 11.0 Hz, J = 1.1 Hz, 1H; CHCHcisH), 2.37 (s, 3H; mesityl-
para-CH3), 2.10 ppm (s, 6H; 2×mesityl-ortho-CH3). 13C NMR (100 MHz, CD2Cl2):  = 147.9 (1C; 8-C), 144.6 (1C;
5-CH), 143.4 (1C; 3-CH), 139.6 (1C; mesityl-para-CCH3), 136.8 (2C; 2×mesityl-ortho-CCH3), 136.2 (1C; 8a-C),
136.2 (1C; 7a-C), 133.1 (1C; 2-CCH), 130.5 (1C; 7-CH), 130.1 (1C; mesityl-C), 128.7 (2C; 2×mesityl-CH), 128.4
(1C; CHCHH), 125.6 (1C; 1-CH), 119.1 (1C; 6-CH), 114.9 (1C; CHCHH), 21.4 (1C; mesityl-para-CH3), 20.2 ppm
(2C; 2×mesityl-ortho-CH3). 19F NMR (376 MHz, CD2Cl2):  = −145.9 ppm (q, JBF = 29 Hz, 2F; BF2). 11B NMR
(128 MHz, CD2Cl2):  = 0.34 ppm (t, JBF = 29 Hz, 1B; BF2). MS (ESI): m/z = 359 ([M+Na]+), 337 ([M+H]+), 317
([M−F]+). HRMS (ESI): m/z calcd for C20H20BF2N2 ([M+H]+): 337.1682; found: 337.1681. UV/Vis (CH2Cl2):

abs ([rel]) = 388 (0.32), 541 nm (1); em (ex = 535 nm) = 582 nm.
B – NMR spectra (1H, 13C, 11B, 19F) of BODIPYs and DYEmers 1–8, 10–12, 15–26, S2, S3, S5,
and S8
Figure S1. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 1.
9

Figure S2. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 1.
Figure S3. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 2.
Figure S4. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 2.
10

Figure S5. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 3.
Figure S6. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 3.
Figure S7. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 4.
11

Figure S8. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 4.
Figure S9. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 5.
Figure S10. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 5.
12

Figure S11. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 6.
Figure S12. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 6.
Figure S13. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 7.
13

Figure S14. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 7.
Figure S15. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 8.
Figure S16. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 8.
14

Figure S17. 1H NMR spectrum (CD2Cl2, 600 MHz) of 10.
Figure S18. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 10.
Figure S19. 1H NMR spectrum (CD2Cl2, 600 MHz) of 11.
15

Figure S20. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 11.
Figure S21. 1H (CD2Cl2, 400 MHz; left) and 13C NMR spectra (CD2Cl2, 100 MHz; right) of 12.
Figure S22. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 12.
16

Figure S23. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 15.
Figure S24. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 15.
Figure S25. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 16.
17

Figure S26. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 16.
Figure S27. 1H (CDCl3, 600 MHz; left) and 13C NMR spectra (CDCl3, 150 MHz; right) of 17.
18

Figure S28. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 17.
Figure S29. 1H (CD2Cl2, 400 MHz; left) and 13C NMR spectra (CD2Cl2, 100 MHz; right) of 18.
Figure S30. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 18.
19

Figure S31. 1H NMR spectrum (CDCl3, 200 MHz) of 19.
Figure S32. 11B (CDCl3, 96 MHz; left) and 19F NMR spectra (CDCl3, 188 MHz; right) of 19.
Figure S33. 1H (CDCl3, 600 MHz; left) and 13C NMR spectra (CDCl3, 150 MHz; right) of 20.
20

Figure S34. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 20.
1
Figure S35. H (CDCl3, 400 MHz; left, enlargements for vinylic proton signals) and 13C NMR spectra (CDCl3,
100 MHz; right) of 21.
Figure S36. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 21.
21

1
Figure S37. H (C6D6, 400 MHz; left, enlargements for vinylic proton signals) and 13C NMR spectra (C6D6,
100 MHz; right) of 22.
Figure S38. 11B (C6D6, 128 MHz; left) and 19F NMR spectra (C6D6, 376 MHz; right) of 22.
1
Figure S39. H (CD2Cl2, 400 MHz; left, enlargements for vinylic proton signals) and 13C NMR spectra (CD2Cl2,
100 MHz; right) of 23.
22

Figure S40. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 23.
Figure S41. 1H (CD2Cl2, 600 MHz; left) and 13C NMR spectra (CD2Cl2, 150 MHz; right) of 24.
Figure S42. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 24.
23

Figure S43. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of 25.
Figure S44. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of 25.
Figure S45. 1H (CD2Cl2, 400 MHz; left) and 13C NMR spectra (CD2Cl2, 150 MHz; right) of 26.
24

Figure S46. 11B (CD2Cl2, 128 MHz; left) and 19F NMR spectra (CD2Cl2, 376 MHz; right) of 26.
Figure S47. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of S2.
Figure S48. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of S2.
25

Figure S49. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of S3.
Figure S50. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of S3.
Figure S51. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of S5.
26

Figure S52. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of S5.
Figure S53. 1H (CDCl3, 400 MHz; left) and 13C NMR spectra (CDCl3, 100 MHz; right) of S8.
Figure S54. 11B (CDCl3, 128 MHz; left) and 19F NMR spectra (CDCl3, 376 MHz; right) of S8.
Notes to the 19F NMR spectra of the F-BODIPY compounds:
The additional small signal, which is slightly high-field shifted relative to the main quartet signal (coupling with the
11B nucleus), is due to the coupling with the 10B nucleus (and not an impurity). For the spectra of the compounds S8,
6–8, 15–17, 22, 23, and 26, this ideally septet signal is better resolved than in the spectra of the other compounds,
where it is completely overlaid.
For the compounds S2, S3, and 2 (all meso-ethyl iodo BODIPYs), the two fluorine atoms of the BF2 group are
obviously not equivalent due to different chromophore sides.
27

C – Optical spectra of DYEmers 11 and 17.
Figure S55. Absorption and emission spectra of DYEmer 11 (left) and 17 (right) recorded in CH2Cl2.
D – Cyclic voltammogram of DYEmer 10.
Figure S56. Cyclic voltammogram of DYEmer 10 (500 mV s−1) in CH2Cl2 containing nBu4NPF6 (0.19 mol L−1) at
red12
ox1
½
ox2
½
room temperature.
E
= −1.56 V,
E
= 0.62 V, and
E
= 0.93 V vs. Fc+/Fc.
½
References:
[SI1]
M. Shah, K. Thangaraj, M.-L. Soong, L. T. Wolford, J. H. Boyer, I. R. Politzer, T. G. Pavlopoulos,
Heteroat. Chem. 1990, 1, 389–399.
[SI2]
[SI3]
[SI4]
[SI5]
A. B. Nepomnyashchii, M. Bröring, J. Ahrens, A. J. Bard, J. Am. Chem. Soc. 2011, 133, 8633–8645.
L. Fu, F.-L. Jiang, D. Fortin, P. D. Harvey, Y. Liu, Chem. Comm. 2011, 47, 5503–5505.
T. Rohand, E. Dolusic, T. H. Ngo, W. Maes, W. Dehaen, ARKIVOC 2007, 307–324.
Y. Hayashi, S. Yamaguchi, W. Y. Cha, D. Kim, H. Shinokubo, Org. Lett. 2011, 13, 2992–2995.
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