10.1002/chem.201800165
Chemistry - A European Journal
FULL PAPER
tetrachlorosilane (1.1 mL, 10 mmol, 50 eq.) was slowly added.
The reaction mixture was stirred at 60 °C for 40 h. Then, the
reaction mixture was washed twice with NaOH aq. (2 × 50 mL, 1
M) and extracted with dichloromethane. The organic extract was
neutralized with NH4Cl aq. and washed with brine. The organic
extract was dried over anhydrous Na2SO4. After the solvent was
removed under reduced pressure, the residue was purified by
silica gel chromatography using n-hexane/ethyl acetate (6:4) as
an eluent. Recrystallization from dichloromethane/n-hexane
afforded 2c (0.10 mmol, 74 mg, 50%).
5,15-C6F5), –135.52 (d, J = 26.3 Hz, 1F, o-F of 10-C6F5), –
136.90 (d, J = 26.3 Hz, 2F, o-F of 5,15-C6F5), –137.31 (d, J =
17.5 Hz, 1F, o-F of 10-C6F5), –152.37 (t, J = 21.9 Hz, 2F, p-F of
5,15-C6F5), –152.68 (t, J = 21.9 Hz, 1F, p-F of 10-C6F5), –161.23
(t, J = 21.9 Hz, 2F, m-F of 5,15-C6F5), –161.65 (t, J = 21.9 Hz,
1F, m-F of 10-C6F5), –162.77 (t, J = 21.9 Hz, 2F, m-F of 5,15-
C6F5), –163.84 (t, J = 21.9 Hz, 1F, m-F of 10-C6F5); 29Si-NMR
(CDCl3) δ = –165.69 ppm; HRMS m/z = 1659.0547 (calcd. for
[C74H16ON8F30Si2]+; [M+H]+, m/z = 1659.0579); UV/Vis (CH2Cl2):
λmax / nm (ε / M–1 cm–1) = 389 (5.01´105) and 562 (3.24´104);
Fluorescence (λex = 389 nm, CH2Cl2): λmax = 647 nm, ΦF = 7.0%,
τ = 7.2 ns.
1
2c : H NMR (DMSO-d6) δ / ppm = 9.72 (d, J = 4.1 Hz, 2H, b),
9.35 (d, J = 5.0 Hz, 2H, b), 9.30 (d, J = 4.6 Hz, 2H, b), 9.06 (d, J
= 13.8 Hz, 2H, Py), 8.96 (d, J = 5.0 Hz, 2H, β), 8.25 (s, 1H, Py),
8.19 (s, 1H, Py), –0.26 (s, 1H, Si-OH); 19F NMR (DMSO-d6) δ /
ppm = –138.61 (d, J = 26.3 Hz, 2F, o-F), –139.09 (d, J = 26.3 Hz,
2F, o-F), –154.29 (t, J = 21.9 Hz, 2F, p-F), –162.42 (t, J = 26.3
Hz, 2F, m-F), –162.52 (t, J = 26.3 Hz, 2F, m-F); 29Si NMR
(CDCl3) δ = –148.82 ppm; HRMS m/z = 750.0791 (calcd. for
[C36H13ON5F10Si]+; [M+H]+, m/z = 750.0802); UV/Vis (CH2Cl2):
λmax / nm (ε / M–1 cm–1) = 383 (5.52´104), 405 (3.52´105), 526
(1.29´104), and 563 (3.21´104); Fluorescence (λex = 405 nm,
CH2Cl2): λmax / nm = 571, 621, ΦF = 13.0%, τ = 4.1 ns.
Acknowledgements
The works at Kyoto and Kyushu were supported by Grant-in-Aid
from JSPS (Nos. JP25220822, JP26810021, JP16H00909 and
JP17H05160). The work at Yonsei was supported by the Global
Research Laboratory (GRL) Program funded by the Ministry of
Science, ICT & Future, Korea (2013K1A1A2A02050183).
Synthesis
of
5,15-Bis(pentafluorophenyl)-10-
(triisopropylsilylethynyl))corrole Si(IV) complex (2d).
Conflict of interest
5,15-Bis(pentafluorophenyl)-10-(triisopropylsilylethynyl)corrole
1d (0.20 mmol, 167 mg) was dissolved in 1,2-dichloroethane (30
mL, 6.7 mM) and DIPEA (5.2 mL, 30 mmol, 150 eq.) to which
tetrachlorosilane (1.1 mL, 10 mmol, 50 eq.) was slowly added.
The reaction mixture was stirred at 60 °C for 40 h. Then, the
reaction mixture was washed twice with NaOH aq. (2 × 50 mL, 1
M) and extracted with dichloromethane. The organic extract was
neutralized with NH4Cl aq. and washed with brine. The organic
extract was dried over anhydrous Na2SO4. After the solvent was
removed under reduced pressure, the residue was purified by
silica gel chromatography using n-hexane/dichloromethane (2:8)
as an eluent. Recrystallization from dichloromethane/n-hexane
afforded 2d (0.18 mmol, 153 mg, 87%).
The authors declare no conflict of interest.
Keywords: corrole • silicon complex • X-ray diffraction analysis •
fluorescence • excited-state dynamics
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1
2d: H NMR (CDCl3) δ / ppm = 9.77 (d, J = 4.8 Hz, 2H, β), 9.45
(d, J = 4.1 Hz, 2H, β), 9.08 (d, J = 4.8 Hz, 2H, β), 8.98 (d, J = 4.1
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i
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Hz, 2H, β), 1.49 (m , 3H, Pr), 1.44 (d, J = 6.2 Hz, 18H, Pr), –
4.33 (s, 1H, Si-OH); 19F NMR (CDCl3) δ / ppm = –136.26 (d, J =
26.3 Hz, 2F, o-F), –137.15 (d, J = 26.3 Hz, 2F, o-F), –152.00 (t,
J = 21.9 Hz, 2F, p-F), –161.17 (t, J = 21.9 Hz, 2F, m-F), –161.29
(t, J = 17.5 Hz, 2F, m-F); 29Si NMR (CDCl3) δ = –149.24 ppm;
HRMS m/z = 853.1845 (calcd. for [C42H30ON4F10Si2]+; [M+H]+,
m/z = 853.1871); UV/Vis (CH2Cl2): lmax / nm (ε / M–1 cm–1) = 395
(5.37´104), 418 (3.49´105), 526 (1.08´104), 540 (1.20´104), 567
(1.12´104), and 585 (1.58´104); Fluorescence (λex = 418 nm,
CH2Cl2): λmax / nm = 587, 642, ΦF = 14.0%, τ = 5.8 ns
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Synthesis of μ-Oxo Silicon(IV) Corrole Dimer (3a).
Silicon complex 2a (0.20 mmol, 168 mg) was dissolved in dry
pyridine (0.2 mM). Methanesulfonyl chloride (7.8 μL, 0.10 mmol,
0.5 eq.) was slowly added to the solution. The reaction mixture
was stirred at 100 °C for 5 h. After the solvent was removed
under reduced pressure, the residue was purified by silica gel
chromatography using n-hexane/dichloromethane (1:1) as an
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M. Kadish, Chem. Commun. 2015, 51, 2411; c) G. Lu, J. Li, S. Yan, C.
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eluent.
Recrystallization
from
dichloromethane/n-hexane
afforded 3a (61.8 mg, 37%).
1
3a H-NMR (CDCl3) δ / ppm = 9.04 (d, J = 4.1 Hz, 4H, β), 8.46
(d, J = 4.1 Hz, 4H, β), 8.43 (d, J = 4.6 Hz, 4H, β), 8.22 (d, J = 4.6
Hz, 4H, β); 19F-NMR (CDCl3) δ / ppm = –134.66 (brs, 2F, o-F of
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