Electronic Supplementary Material (ESI) for Analytical Methods.

This journal is © The Royal Society of Chemistry 2018

Electronic Supplementary Information (ESI)

for:
Ultrasensitive and Direct Fluorescencent Detection of RDX Explosive

Vapor via Side-chain Terminal Functionalization of Polyfluorene Probe

Xin Peng,a,b,c Huan Liu,a Ao Liu,a,c Wei Xu,a,c ,Yanyan Fu,a,c Qingguo He,a* Huimin Caoa and Jiangong
Chenga*
a. State Key Lab of Transducer Technology, Shanghai Institute of Microsystem and Information
Technology, Chinese Academy of Sciences, Changning Road 865, Shanghai 200050, China. E-mail:
hqg@mail.sim.ac.cn, jgcheng@mail.sim.ac.cn; Fax: +86-21-62524192; Tel: +86-21-62511070
b. School of Physical Science and Technology, ShanghaiTech University, Middle Huaxia Road 393,
Shanghai, 201210, China.
c. University of the Chinese Academy of Sciences, Yuquan Road 19, Beijing, 100039, China.

Figure S1 single crystal pattern of RDX

BocHN NHBoc
O
Bu4NBr
Br Br Br 1
N O
H NaOH/toluene

Br Br

BocHN NHBoc
O O
O O B B PF6-Boc
B B O O
O O 1 Reflux

Pd(PPh3)4/ K2CO3
2
PdCl2(dppf)/KOAc Toluene/H2O(2:1)
DMSO, 80℃ , 12h n
BocHN NHBoc

Monomer 11:
To a round-bottomed single-necked flask was added 2,7- dibromofluorene (1.62 g, 5 mmol), tert-
butyl 6-bromohexylcarbamate (3.05 g, 11 mmol), sodium hydroxide solution (40%, 25 mL),
Bu4NBr (0.32 g, 1 mmol), and toluene (40 mL). The reaction mixture was stirred at 85 °C for 12 h
and worked up. The reaction mixture was then extracted with water. The organic layer was
separated, dried over MgSO4, and concentrated for column chromatography. The crude product was
purified on a silica gel column by eluting with CH2Cl2. The desired fractions were collected and
concentrated to afford 1.88 g (52%) of monomer 1 (white solid). 1H NMR (500Hz, Chloroform-d)
δ 7.53 – 7.41 (m, 6H), 4.41 (s, 2H), 3.09 – 2.90 (m, 4H), 2.04–1.83 (m, 4H), 1.42 (s, 18H), 1.12 –
1.01 (m, 8H), 0.58 (ddt, J = 9.4, 7.0, 4.0 Hz, 4H). 13C NMR (101 MHz, Chloroform-d) δ 152.36,
139.13, 130.33, 126.16, 121.57, 121.25, 55.65, 40.52, 40.13, 29.98, 29.54, 28.47, 26.44, 23.63.
Monomer 22：
A mixture of 2,7-bibromo-9,9-bis(60-butoxylcarbonylaminohexyl) fluorene (1 g, 1.38 mmol),
KOAc (0.9 g, 9.2mmol), bis(pinacolato)diborane (0.78 g, 3.1mmol), Pd(dppf)Cl2 (80 mg,
0.11mmol) in 20mL DMSO was stirred at 80 °C for 12 h. After cooled to room temperature, water
and chloroform were added into the mixture. The separated organic layer was washed with brine,
water and dried over anhydrous MgSO4. After removal of the solvent under reduced pressure, the
residue was purified over column chromatography with petroleum ether/ethyl acetate (3:1) as the
eluent to give Monomer 2 as a white solid (0.6 g, 52%). 1H NMR (500 MHz, Chloroform-d) δ 7.80
(d, J = 7.4 Hz, 2H), 7.72 (s, 4H), 4.43 (s, 2H), 2.96 (q, J = 7.3, 6.7 Hz, 4H), 2.03 – 1.95 (m, 4H),
1.40 (d, J = 9.5 Hz, 42H), 1.23 (d, J = 6.0 Hz, 4H), 1.03 (p, J = 3.6 Hz, 8H), 0.54 (dq, J = 12.0, 4.9,
2.9 Hz, 4H).
Synthesis of PF8:
2,7-dibromo-9,9-dioctyl-9H-fluorene (546 mg, 1 mmol), 2,2'-(9,9-dioctyl-9H-fluorene-2,7-
diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (642 mg, 1 mmol), Pd (PPh 3)4 (44.11 mg, 0.043
mmol) was weighed and degassed. K2CO3 (aq., 2M/L, 5 mL) and 10 mL of toluene were added
under argon protection and the mixture was stirred at 120 °C. for 72 hours. The solution was washed
with water and extracted with dichloromethane to give the crude product after removal of the
solvent. The crude product was dissolved in dichloromethane and precipitated in methanol to give
a gray green solid (0.45 g, yield 57%). 1H NMR (500 MHz, Chloroform-d) δ 7.83 (t, J = 7.1 Hz,
2H), 7.68 (q, J = 13.0, 10.0 Hz, 4H), 2.09 (d, J = 29.9 Hz, 4H), 1.17 (d, J = 33.0 Hz, 20H), 0.82 (dd,
J = 9.1, 4.8 Hz, 10H). 13C NMR (101 MHz, Chloroform-d) δ 151.89, 140.58, 140.10, 126.23, 121.57,
120.03, 77.01, 55.41, 40.45, 31.86, 30.10, 29.28, 23.99, 22.66, 14.12. Mn =23733, Mw = 57671,
PDI = 2.43 based on GPC analysis.
Synthesis of PF6-Boc:
Following the same polymerization procedure as PF8, with monomer 1 (360mg, 0.5 mmol)
and monomer 2 (408 mg, 0.5 mmol). The resulting product was isolated as slightly gray solid ( 338
mg, 60%). H NMR (500 MHz, Chloroform-d) δ 7.85 (t, J = 7.2 Hz, 1H), 7.77 – 7.59 (m, 2H), 4.54
1

(s, 1H), 3.00 (q, J = 6.9 Hz, 2H), 2.13 (s, 2H), 1.40 (d, J = 3.8 Hz, 9H), 1.31 (dt, J = 18.8, 8.7 Hz,
2H), 1.15 (s, 4H), 0.82 (s, 2H). 13C NMR (101 MHz, Chloroform-d) δ 155.96, 151.62, 140.26 (d, J
= 35.5 Hz), 126.25, 121.31, 120.14, 78.89, 77.24, 55.32, 40.50, 29.90 (d, J = 23.3 Hz), 28.43, 26.56,
23.98. GPC: Mn= 26790, Mw= 67513, PDI= 2.52 based on GPC analysis.
Figure S2 1H NMR spectrum of Monomer 1 in CDCl3

Figure S3 13C NMR spectrum of Monomer 1 in CDCl3

Figure S4 1H NMR spectrum of Monomer 2 in CDCl3

Figure S5 1H NMR spectrum of Monomer 2 in CDCl3

Figure S6 1H NMR spectrum of PF8 in CDCl3

Figure S7 13C NMR spectrum of PF8 in CDCl3

Figure S8 1H NMR spectrum of PF6-BOC in CDCl3

Figure S9 13C NMR spectrum of PF6-BOC in CDCl3

 0.0015
0.0002 PF8
a PF6-boc b
0.0010 0.0001

Current/A
Current/A

0.0005 0.0000

-0.0001
0.0000
-0.0002

-0.0005
-0.0003

-0.0010 -0.0004
-2 -1 0 1 2 -3 -2 -1 0 1 2 3
Voltage/V Voltage/V

0.00005
0.00000 c
-0.00005
-0.00010 RDX
Current/A

-0.00015
-0.00020
-0.00025
-0.00030
-0.00035
-0.00040
-2 -1 0 1 2
Voltage/V

Figure S10 The CV curves of PF6-Boc (a) PF8 (b) and RDX(c) in CH3CN solution at a sweep rate of
100 mV/s.
HOMO=-e (Eoxonset + 4.741) (eV), LUMO=-e (Eredonset + 4.741) (eV), ⊿E =LUMO-HOMO.
RDX : Eredonset=-0.973(V), LUMO=-3.76(eV)
PF6-Boc: Eredonset=-1.977(V), LUMO=-2.76(eV); Eoxonset=1.15(V), HOMO=-5.89(eV);⊿E=3.13(eV)
PF8 : Eredonset=-2.17(V), LUMO=-2.57(eV); Eoxonset=1.35(V), HOMO=-6.11(eV); ⊿E=3.54(eV)

PF-8 film
1.0
b PF-8 solution
Norm.Abs.Int.(a.u)

Norm.PL.Int.(a.u)

0.8

0.6

0.4

0.2

0.0

300 350 400 450 500 550

Wavelength(nm)

Figure S11 UV−vis absorption and emission spectra of PF8 in solution and in film state
 Quenching Photobleaching

1 0.01
0.9 0.04
0.01
0.02
0.8
0.01
0.7
0.6
0.5 0.9
0.76 0.8 0.8
0.4 0.68
0.3
0.2
0.1
0
Tol 2mg/ml THF 2mg/ml DCM 2mg/ml DCM 1mg/ml DCM 0.5mg/ml

Figure S12 Photobleaching of PF6-Boc films prepared with different solvents and concentrations and
their fluorescence quenching response to RDX saturated vapor.

Figure S13 Infrared spectra of PF6-Boc films before and after exposure to RDX vapor

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