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Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
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ARTICLE
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(
td, J = 8.3 Hz, J = 1.6 Hz, 1H), 7.31 (dd, J = 7.5 Hz, J = 1.6 Hz, 1H), 4,4-difluoro-8-(2-nitrophenyl)-4-bora-3a,4a-diazaV-isew-inArdtiacleceOnnleine
DOI: 10.1039/D0NJ02576C
(10). Column chromatography using hexane/ethyl acetate (8:2)
7
2
1
1
2
2
.08‒7.03 (m, 2H), 6.80 (d, J = 4.0 Hz, 2H), 6.48 (d, J = 4.0 Hz,
1
3
20
1
H), 3.75 (s, 3H). C NMR [100 MHz, CDCl3] (δ, ppm): 157.2, afforded 10 as an orange solid (14%). Mp: 198 °C H NMR [500
44.5, 143.8, 135.7, 131.6, 131.5, 131.1, 122.4, 120.1, 118.1, MHz, CDCl ] (δ, ppm): 8.22 (dd, J = 7.8, 1.6 Hz, 1H), 7.95 (s, 2H),
3
11
11.3, 55.6. B NMR [128 MHz, CDCl
3
] (δ, ppm): 0.31 (t, JB-F
] (δ, ppm): -144.47 (dq, JB-Fa
=
=
7.84 – 7.69 (m, 2H), 7.57 (dd, J = 7.4, 1.6 Hz, 1H), 6.67 (d, J = 4.2
8 Hz). 19F NMR [376 MHz, CDCl
Hz, 2H), 6.51 (d, J = 4.3 Hz, 2H). C NMR [125 MHz, CDCl
13
3
3
] (δ,
8 Hz, JF-F = 104 Hz), -145.63 (dq, JB-Fb = 28 Hz, JF-F = 104 Hz).
ppm): 149.1, 145.3, 142.6, 134.6, 133.2, 132.3, 131.3, 129.8,
11
1
28.4, 125.2, 119.2. B NMR [160 MHz, CDCl
Hz). 19F [470 MHz, CDCl
3
] δ -0.69 (t, J = 28
] δ -143.92 (dq, JB-Fa = 28 Hz, JF-F = 104
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4
,4-difluoro-8-(2,4-dimethoxyphenyl)-4-bora-3a,4a-diaza-s-
3
indacene
(
6
)
.
Column chromatography using hexane/ethyl Hz), - 146.32 (dq, JB-Fb = 28 Hz, JF-F = 104 Hz).
as a red powder (25%). Mp: 156–157
acetate (8:2) afforded
6
-
1
°C. FTIR-ATR (ʋ, cm ): 3108, 2937, 1383, 1255, 1167, 1110, 4,4-difluoro-8-(1-pyrenyl)-4-bora-3a,4a-diaza-s-indacene
(
11
)
.
1
1
063, 979, 837, 780, 746, 706, 618, 582, 420. H NMR [400 MHz, Column chromatography using hexane/ethyl acetate (9:1)
17
3
CDCl ] (δ, ppm): 7.87 (s, 2H), 7.24 (d, J = 9 Hz, 1H), 6.83 (d, J = afforded 11 as a green crystalline powder (20% yield). Mp:
1
3
.6 Hz, 2H), 6.59 (d, J = 6.4 Hz, 2H), 6.47 (d, J = 3.6 Hz, 2H), 3.89 134
−
135 °C. H NMR [400 MHz, CDCl
3
] (δ, ppm): 8.3 – 8.0 (m,
13
13
(
s, 3H), 3.73 (s, 3H). C NMR [100 MHz, CDCl
3
] (δ, ppm): 162.7, 11H), 6.62 (d, J = 4.2 Hz, 2H), 6.46 (d, J = 3.0 Hz, 2H). C NMR
1
9
F
3
58.7, 144.6, 144.3, 136.4, 132.9, 131.5, 117.9, 115.3, 104.3, [100 MHz, CDCl ] (δ, ppm): 146.6, 144.5, 136.6, 132.6, 131.8,
1
1
9.0, 55.6, 55.5. B NMR [128 MHz, CDCl
= 29 Hz). 19F NMR [282 MHz, CDCl
3
] (δ, ppm): 0.29 (t, JB- 131.4, 130.8, 130.5, 129.1, 128.6, 127.9, 127.9, 127.2, 126.7,
11
3
] (δ, ppm):
145.72 (dq, JB-Fb = 29 Hz, JF-F = 107 Hz). MHz, CDCl
HRMS-ESI-TOF: Experimental mass for C17 15BFN m/z CDCl ] (δ, ppm):
15BFN
−
144.56 (dq, JB- 126.3, 126.0, 125.0, 124.6, 124.3, 124.1, 118.9 B NMR [160
Fa = 29 Hz, JF-F = 107 Hz),
−
3
] (δ, ppm): -0.06 (t, JB-F = 28 Hz). 19F NMR [282 MHz,
144.51 (dq, JB-Fa = 28 Hz, JF-F = 104 Hz), 145.26
H
2
O
2
3
−
−
3
09.120512; calculated m/z 309.1211 for C17
H
2
O
2
; % (dq, JB-Fb = 28 Hz, JF-F = 104 Hz).
+
error: 0.361884; [M−F]
4
,4-difluoro-8-(2-hydroxyphenyl)-4-bora-3a,4a-diaza-s-
Computational Methodology
indacene Column chromatography using hexane/ethyl
(7).
All calculations were carried out taking hexane as solvent, trying
to match or correlate experimental observations in a solvent
with good emission properties and discarding toluene to avoid
possible π-stacking interactions with the studied species.
3
8
acetate (8:2) afforded
7
as a green powder (10%). Mp: 134–
] (δ, ppm): 7.89 (s, 2H), 7.4 (td,
= 1.7 Hz, 1H),
.04 – 6.89 (m, 2H), 6.90 (d, J = 3.6 Hz, 2H), 6.49 (d, J = 3.9 Hz,
H). C NMR [75 MHz, CDCl
35.2, 132.1, 131.6, 120.4, 120.1, 120.0, 119.0, 117.1. B NMR
1
1
36 °C. H NMR [300 MHz, CDCl
3
J = 7.2 Hz, J = 1.7 Hz, 1H) 7.25 (dd, J = 7.7 Hz, J
2
7
2
1
Geometry optimizations were carried out through all-electron
calculations using the B3LYP hybrid functional at the def2SVP
theory level using the SMD solvation approach, to obtain the
geometries of lowest energy for the studied species and to
analyze important structural details. Regarding the
computation of rotational barriers, all geometries were re-
optimized with the M06-2X hybrid functional and the def2SVP
basis set using the SMD solvation model to refine the
computation of energetics. Scans through redundant
coordinates for the dihedral angle between the BODIPY and the
meso substituents were done using M06-2X/def2SVP approach
with the SMD solvation model. Being this combination a proven
approach in the field of thermochemistry, energetics, energy
13
3
] (δ, ppm): 153.6, 144.8, 143.0,
11
1
9
[
160 MHz, CDCl
3
] (δ, ppm): -0.28 (t, JB-F = 28 Hz). F NMR [282
3
MHz, CDCl ] (δ, ppm): 143.72 (dq, JB-Fa = 28 Hz, JF-F = 104 Hz),
−
−
144.94 (dq, JB-Fb = 28 Hz, JF-F = 104 Hz).
4
,4-difluoro-8-(2-chlorophenyl)-4-bora-3a,4a-diaza-s-
indacene Column chromatography using hexane/acetone
as an orange-green crystalline solid (23%). Mp:
03 °C. H NMR [400 MHz, CDCl ] (δ, ppm): 7.94 (s, 2H), 7.58 –
.52 (m, 1H), 7.52 – 7.45 (m, 1H), 7.43 – 7.35 (m, 2H), 6.73 (d, J
(8).
(
9:1) afforded 8
1
1
7
=
3
1
3
3
4.1 Hz, 2H), 6.51 (d, J = 4.1 Hz, 2H). C NMR [100 MHz, CDCl ]
(
δ, ppm): 145.1, 143.5, 135.4, 133.3, 132.5, 131.6, 131.2, 131.2,
39–41
barriers, among other features.
1
1
1
30.3, 126.6, 118.9. B NMR [128 MHz, CDCl
3
] δ -0.68 (t, J = 28
] δ -144.47 (dq, JB-Fa = 28 Hz, JF-F = 105
The energy maximum of each corresponding scan was then
optimized as a transition state (TS) to determine the real
geometry and rotational barrier of such TSs. This was done also
with the M06-2X/def2SVP theory level and SMD solvation
approach. Time-dependent Density Functional Theory (TD-DFT)
calculations were run using the same functional at the 6-
Hz). 19F [376 MHz, CDCl
3
Hz), - 145.67 (dq, JB-Fb = 28 Hz, JF-F = 105 Hz). ES-MS:
+
(
15
C H
10BClF
2
N
2
) 283.5 [M – F].
4
,4-difluoro-8-(2-fluorophenyl)-4-bora-3a,4a-diaza-s-indacene
(
9
)
.
Column chromatography using hexane/ethyl acetate (9:1)
3
11g(d,p) theory level with the CPCM solvation method, to
obtain the value for the dipole moment corresponding to the
main transition (S → S ) for all BODIPY derivatives.
After determining the orbital behavior of the S → S
the energetic evolution of S was calculated at the M06-
X/def2SVP theory level using the SMD solvation method in
1
afforded
CDCl
Hz, 2H), 6.18 (d, J = 4.0 Hz, 2H). 19F NMR [84.7 MHz, CDCl
10.86 (s), -143.88 (dq, JB-Fa = 28 Hz, JF-F = 104 Hz), - 145.35 (dq,
B-Fb = 28 Hz, JF-F = 104 Hz).
9
as a red crystalline solid (16%). H NMR [90 MHz,
3
] (δ, ppm): 7.49 (s, 2H), 7.24 – 6.77 (m, 4H), 6.51 (d, J = 3.8
] δ -
0
1
3
0
1
transition,
1
J
1
2
hexane, by TDDFT approach to the most representative points
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