E
Synthesis
Q. Huang et al.
Paper
Job Plot Analysis
All solvents used for syntheses were dried by distillation under nitro-
gen prior to use. THF and 1,4-dioxane were distilled under nitrogen
after reflux over sodium. Other chemicals were obtained from com-
mercial suppliers (Innochem or Acros). Air-sensitive reactions were
carried out under argon or nitrogen atmospheres. C60 (99.9%) and C70
A solution of the C60 or C70 guest in toluene and a solution of MC3 in
toluene were mixed in different ratios to prepare 11 samples ([guest]
+ [MC3] = 6.67 × 10 M). The UV-vis absorption spectra were record-
ed for each sample, and the absorption changes at 340 nm were mon-
itored for the Job plot analysis.
–6
(99.9%) fullerenes were purchased from Suzhou Dade Carbon Nano-
technology Co., Ltd. 7,10-bis[4-(4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lan-2-yl)phenyl]fluoranthene (6)14 and compound 10 were synthe-
sized according to the reported procedures. IR spectra were recorded
using a spectrophotometer. NMR spectra were recorded on a Bruker
11
Fluorescence Quenching Experiments
Fluorescence quenching was studied by the addition of one fullerene
guest to MC3. To a solution of MC3 (1 × 10 M) in toluene was added
a solution of the guest in toluene (1 × 10 M) at 25 °C. The changes in
the fluorescence intensity of MC3 were measured at 488 nm. The
Stern–Völmer constant (KSV) was determined by using equation 1:
–5
1
13
BioSpin ( H, 400 MHz; C, 100 MHz) spectrometer. Chemical shifts
–3
1
(
7
) are reported in ppm relative to CDCl (7.26 ppm for H NMR and
3
13
7.0 ppm for C NMR). Data are reported as follows: chemical shift,
multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet), cou-
pling constant (Hz), integration. High-resolution mass spectrometry
F0/F = 1 + KSV[guest] (eq 1)
(HRMS) was carried out on spectrometer using MALDI-TOF-MS tech-
the binding constant (K ) was determined by using equation 2:
a
niques. UV-vis absorption spectra were obtained using a UNIC-3802
spectrophotometer.
F/F = (1 + (k /k )K [guest])/(1 + K [guest]) (eq 2)
0
f
s
a
a
where F is the fluorescence intensity, F0 is the fluorescence of MC3
before the addition of one fullerene guest, k is the proportionality
f
Compound 11
constant of the complex, and k is the proportionality constant of the
s
To a mixture of 7,10-bis[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
host.
yl)phenyl]fluoranthene (6) (113 mg, 0.186 mmol), compound 1011
(163.32 mg, 0.186 mmol) and potassium hydroxide (134 mg, 2.388
mmol) in a round-bottomed flask (500 mL) were added THF (250 mL),
H O (10 mL), and Pd(PPh ) (30.06 mg, 0.026 mmol) under an argon
Funding Information
2
3 4
atmosphere. Thereafter, the solution was heated at 80 °C for 48 h. Af-
ter cooling to room temperature, the solvent was removed under vac-
This work was financially supported by the National Natural Science
Foundation of China (21473170, 51772285) and the National Key Re-
uum and the remaining aqueous fraction was extracted with CH Cl .
2
2
search and Development Program of China (2017YFA0402800).
N
ati
o
n
a
l Natural S
c
i
e
n
c
e
F
o
u
n
d
ati
o
n
of
C
h
i
n
a
(2
1
4
7
3
1
7
0)Nati
o
n
a
l Natural S
c
i
e
n
c
e
F
o
u
n
d
ati
o
n
of
C
h
i
n
a
(5
1
7
7
2
2
8
5)Nati
o
n
a
lK
e
y
R
esearc
h
a
n
d
D
e
v
e
l
o
p
m
e
ntProgra
m
of
C
h
i
n
a
(2
0
1
7
Y
F
A
0
4
0
2
8
0
0)
The combined organic layer was dried and concentrated under re-
duced pressure to afford crude product 11 as a gray solid that was
used in the next step without further purification.
+
Supporting Information
HRMS (MALDI-TOF): m/z [M] calcd for C76H62O : 1070.4546; found:
6
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1707963.
1070.4538.
S
u
p
p
orit
n
g Inform ati
o
n
S
u
p
p
orit
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g Inform ati
o
n
Molecular Crown MC3
To a round-bottomed flask (50 mL) (vessel A) containing a magnetic
stir bar were added sodium metal (274 mg, 11.9 mmol), anhydrous
THF (12 mL) and naphthalene (1.00 g, 7.82 mmol), and the resulting
mixture was stirred at room temperature for 1 d. To another round-
bottomed flask (200 mL) (vessel B) containing a magnetic stir bar
were added the crude product 11 and dry THF (80 mL). A solution of
sodium naphthalide (2 mL, 2 mmol, 1.0 M in THF) from vessel A was
then added at –78 °C. After stirring the mixture at –78 °C for 2 h, a 1
M solution of I2 in THF (1.5 mL) was added. After warming to room
temperature, the mixture was quenched with aqueous saturated so-
dium thiosulfate, extracted with CH Cl , dried over Na SO , and con-
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2
2
2
4
centrated under reduced pressure. The crude product was purified by
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2
2
20% yield over two steps) as a yellow solid. Mp: >250 °C dec.
IR (KBr): 2960, 2923, 2852, 1741, 1667, 1593, 1482, 1459, 1375, 1263,
–1
1
185, 1158, 1102, 1039, 854, 812, 778, 741 cm .
1
H NMR (400 MHz, CDCl ): = 8.20 (d, J = 6.8 Hz, 2 H), 7.85 (d, J = 8.4
3
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13
C NMR (100 MHz, CDCl ): = 123.08, 126.91, 127.36, 127.70,
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3
1
1
28.74, 132.40, 135.93, 136.15, 136.44, 138.11, 138.18, 139.35,
39.61.
HRMS (MALDI-TOF): m/z [M]+ calcd for C70H44: 844.3443; found:
44.3341.
8
2001, 123, 12770.
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2020. Thieme. All rights reserved. Synthesis 2020, 52, A–F