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A PicoHarp 300 photon processor completed the TCSPC system.
SymPhoTime v. 5.1 analysis software was used for image process-
ing and lifetime fitting. A tail fit with multi-exponential functions
was performed to analyse fluorescence decays of selected regions
of interest (ROI). The system allowed measurement of fluorescence
lifetimes from 300 ps to several nanoseconds.
7.62 (1H), 7.69 (1H), 8.56 ppm (1H); 13C{1H} NMR (75 MHz, CDCl3):
d=29.2, 35.1, 35.5, 71.6, 79.8, 120.7, 121.2, 137.5, 149.3, 159.2,
170.7 ppm; IR (KBr): n˜ =1647.6 cmꢀ1 (C=O); ESI-MS: m/z: 275 [M+
Na]+; elemental analysis calcd (%) for C11H12N2OS2: C 52.35, H 4.79,
N 11.10, S 25.41; found: C 52.41, H 4.65, N 10.77, S 25.07.
Synthesis of the alkyne–BODIPy derivative 18
Synthesis of 3-(tritylthio)propionic acid (1)
4-Pentynoic acid (0.076 g, 0.79 mmol) in CH2Cl2 (5 mL) was added
to a solution of DCC (0.254 g, 1.23 mmol) in CH2Cl2 (5 mL), followed
by the addition of 17 (0.268 g, 0.79 mmol) in CH2Cl2 (4 mL). Anhy-
drous DMAP (0.010 g, 0.079 mmol) was then added and the result-
ing solution was stirred under nitrogen for 24 h at RT. The reaction
mixture was then diluted with CH2Cl2, washed in sequence with
water, a 0.5m solution of HCl (2ꢁ40 mL), a saturated solution of
NaHCO3 (2ꢁ40 mL) and brine. After drying over anhydrous Na2SO4,
the solvent was evaporated and the crude product was purified by
flash chromatography on silica gel, eluting first with EtOAc/hexane
(1:3) and then with EtOAc/hexane (1:2) to afford 18 as an orange
gummy solid (75% yield). 1H NMR (300 MHz, CDCl3): d=1.41 (s,
6H), 2.54 (s, 6H), 2.63 (m, 4H), 5.97 (s, 2H), 7.23 (2H), 7.69 (2H),
7.83 ppm (1H); 13C{1H} NMR (75 MHz, CDCl3): d=14.6, 24.9, 25.5,
33.9, 36.3, 49.3, 53.4, 69.8, 82.8, 120.0, 121.7, 128.7, 130.6, 131.6,
138.7, 141.2, 143.1, 155.4, 169.4 ppm; IR (KBr): n˜ =1658.6 cmꢀ1 (C=
O); elemental analysis calcd (%) for C25H29BF2N3O: N 9.63, C 68.82,
H 6.70; found: N 9.76, C 68.65, H 6.91.
The carboxylic acid derivative 1 was prepared according to a litera-
ture procedure[14] and the final product was isolated in 90% yield
1
as analytically pure white crystals. H NMR (300 MHz, CDCl3, select-
3
3
ed data): d=2.25 (t, J=7.2 Hz, 2H), 2.48 (t, J=7.2 Hz, 2H), 7.23–
7.33 (9H), 7.33–7.45 ppm (6H); elemental analysis calcd (%) for
C22H20O2S: C 75.83, H 5.78, S 9.20; found: C 76.09, H 5.91, S 9.05.
For additional characterisation data, see ref. [14].
Synthesis of N-(prop-2-ynyl)-3-(tritylthio)propanamide (2)
HOBt (2.56 g, 18.9 mmol) and DCC (3.90 g, 18.9 mmol) were added
in sequence to a solution of 1 (6 g, 17.2 mmol) in dry and de-
gassed DMF (120 mL), and the resulting mixture was maintained
under stirring at room temperature for 3 h until completion of the
reaction. The reaction course was followed by TLC (eluent: petrole-
um ether/AcOEt=60/40) to monitor the progressive disappearance
of starting acid 1. Et3N (2.88 mL, 20.6 mmol) and propargylamine
(1.4 mL, 20.6 mmol) were added and the resulting mixture was
stirred at room temperature for 24 h. The reaction was quenched
by adding a dilute solution of HCl (0.05m, 120 mL) followed by
CH2Cl2 (120 mL). The organic mixture was then extracted and the
aqueous phase was treated with brine (120 mL). The aqueous
mother liquors were then extracted three times with CH2Cl2 (3ꢁ
90 mL). The collected organic phases were dried over Na2SO4 and
evaporated to dryness under reduced pressure. The crude semi-
solid material was purified by flash chromatography (SiO2, petrole-
um ether: AcOEt=60:40) to give 2 as a white solid (91% yield).
Homogeneous CuAAC reaction on 3 with the azido-BODYPy
derivative 6
Compound 3 (0.55 mmol), CuSO4 (0.02 mmol) and sodium ascor-
bate (0.04 mmol) were added in sequence to a solution of 6 in dry
and degassed DMF (2 mL). The mixture was stirred for 24 h at
508C under a nitrogen atmosphere. Distilled water (20 mL) was
added and the mixture was extracted with AcOEt (3ꢁ15 mL). The
collected organic phases were washed twice with water (2ꢁ30 mL)
before being dried over Na2SO4 and concentrated under reduced
pressure. The crude material was purified by flash chromatography
over silica gel (eluent: AcOEt/petroleum ether: 80/20) to afford 7
as dark-red crystals (45% yield (93% yield if we consider the recov-
ery of azido reagent 6 during chromatographic purification)). The
reaction was also performed by using CuI[P(OEt)3] as an alternative
soluble CuAAC catalyst under identical experimental conditions,
3
3
1H NMR (300 MHz, CDCl3): d=2.03 (t, J=7.3 Hz, 2H), 2.23 (t, J=
3
2.4 Hz, 1H), 2.53 (t, J=7.3 Hz, 2H), 3.99 (m, 2H), 7.23–7.26 (10H),
7.33–7.46 ppm (5H); 13C{1H} NMR (75 MHz, CDCl3): d=27.5, 29.2,
35.4, 66.9, 71.7, 79.4, 126.8, 128.0, 129.6, 144.6, 170.6 ppm; IR (KBr):
n˜ =1636.4 cmꢀ1 (C=O); elemental analysis calcd (%) for C25H23NOS:
C 77.89, H 6.01, N 3.63, S 8.32; found: C 78.01, H 5.91, N 3.68, S
8.35.
1
without any appreciable improvement in yield. H NMR (300 MHz,
3
CDCl3): d=1.44 (s, 6H), 2.58 (s, 6H), 2.66 (t, J=6.7 Hz, 2H), 3.11 (t,
3
3J=6.7 Hz, 2H), 4.66 (d, J=5.8 Hz, 2H), 6.00 (s, 2H), 7.13 (1H), 7.46
Synthesis of N-(prop-2-ynyl)-3-(pyridin-2-yldisulfanyl)-
(2H), 7.55–7.65 (3H), 7.90 (2H), 8.15 (1H), 8.51 ppm (1H);
13C{1H} NMR (75 MHz, CDCl3): d=14.5, 14.7, 34.7, 35.6, 120.6, 120.9,
121.3, 121.7, 130.0, 131.3, 135.5, 137.1, 137.4, 139.5, 142.9, 146.2,
149.9, 156.2, 159.1, 171.1 ppm; IR (KBr): n˜ =1647.6 cmꢀ1 (C=O); ele-
mental analysis calcd (%) for C30H30BF2N7OS2: C 58.35, H 4.90, N
15.88, S 10.38; found: C 58.41, H 4.65, N 15.77, S 10.07.
propanamide (3)
1,2-Di(pyridin-2-yl)disulfane (10.3 g, 46.8 mmol) and Et3SiH
(2.75 mL, 17.2 mmol) were added in sequence to a solution of 2
(6 g, 15.6 mmol) in dry and degassed CH2Cl2 (140 mL). TFA (35 mL)
was added dropwise to the resulting mixture, and the system was
maintained under stirring at RT for 4 h. The mixture was concen-
trated to a reduced volume and treated with AcOEt/Et3N (1:1;
550 mL). The solution was stirred at room temperature overnight
before being diluted with water (550 mL). The resulting phases
were separated and the aqueous liquor was extracted three times
with AcOEt (3ꢁ500 mL). The collected organic layers were dried
over Na2SO4 and the solvent was removed under reduced pressure.
The crude product was purified by flash chromatography (SiO2,
AcOEt/petroleum ether 80:20) to give 3 as a pale yellow oil (62%
General procedure for the homo- and hetero-derivatisation
of phenylazido-decorated SWCNTs through the CuAAC reac-
tion
The CuAAC protocol used for the homo- and hetero-derivatisation
of 13 to give 14, MIX1 and MIX2 hybrids followed that already de-
scribed by some of us.[11] In a typical procedure, fN3-SWCNTs
(20 mg) were suspended in dry and degassed DMF (3 mL) and so-
nicated for 15 min. The resulting suspension was treated in se-
1
4
yield). H NMR (300 MHz, CDCl3): d=2.26 (t, J=2.6 Hz, 1H), 2.64 (t,
3J=6.7 Hz, 2H), 3.10 (t, 3J=6.7 Hz, 2H), 4.10 (m, 2H), 7.17 (1H),
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