S1

Electronic Supplementary Information (ESI) For

A benzothiadiazole-based fluorescent sensor for selective

detection of oxalyl chloride and phosgene

Wen-Qiang Zhang,‡a Ke Cheng,‡

a Xinyu Yang,

a Qiu-Yan Li,*

a He Zhang,

a Zheng Ma,

a Han Lu,

a Hui Wu

b and

Xiao-Jun Wang*a

aJiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and

Materials Science, Jiangsu Normal University, Xuzhou 221116, P. R. China.

bKey Laboratory of Biotechnology for Medicinal Plants of Jiangsu Province, Jiangsu Normal University, Xuzhou

221116, P. R. China

‡These authors contributed equally to this work.

E-mail: qyli@jsnu.edu.cn (Q.-Y. Li)

E-mail: xjwang@jsnu.edu.cn (X.-J. Wang)

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2017

S2

General method and materials

Unless specifically mentioned, all chemicals are commercially available and were used as received.

NMR spectra were taken on a Bruker AV400 at room temperature. Mass spectra (EI and HRMS)

were obtained in Waters GCT Premier and Bruker MicroToF-Q II spectrometer, respectively.

Fluorescence spectra and UV-vis spectra were recorded at room temperature on an Agilent Cary

Eclipse spectrofluorophotometer and PerkinElmer Lambda 365, respectively.

Quantum yield measurements

Fluorescence quantum yields were determined in the reference of quinine sulfate (Ф = 0.54) in

0.1M H2SO4 at 350 nm excitation.[S1]

The quantum yields are calculated according to following

equation.

Фx = Фs (AsSx)/(AxSs) (nx/ns)2

Ax and As are the absorbance of samples and the standard. Sx and Ss are integrated fluorescence

emission corresponding to samples and the standard. n is the refractive index of the solvent.

Table S1 Photophysical data of BTA, BTAH and BTAP.

Compound Absorbance, λmax (nm) Emission, λmax (nm) Quantum Yield (Φ)

BTA 438 522 0.06

BTAH 493 516 0.78

BTAP 492 508 0.56

S3

Fig. S1 UV-vis absorption spectra of BTA, BTAP and BTAH (10 μM) in DCM at room temperature.

Fig. S2 (a) Fluorescence spectra of BTAH solution (1 M) and BTA (1 M) solution upon addition of oxalyl

chloride (5 M) in DCM. (b) Fluorescence spectra of BTAP solution (5 M) and BTA (5 M) solution upon

addition of triphosgene (50 M) and TEA (20M) in DCM. (λex = 380 nm).

300 400 500 600

0.0

0.2

0.4

0.6

0.8

1.0

Ab

so

rba

nc

e

Wavelength / nm

BTA

BTAP

BTAH

400 500 600 700

0

100

200

300

BTA+oxalyl chloride

BTA

BTH

Inte

nsit

y

Wavelength / nm

a

400 500 600 700

0

50

100

150

BTA+Triphosgene+TEA

BTP

BTA

Inte

nsit

y

Wavelength / nm

b

S4

Details of Assay Experiments

Preparation of phosgene: As a toxic gas, phosgene is danger to use directly. We employed

triphosgene, which is a common nonvolatile and less toxic precursor, to produce phosgene in the

presence of tertiary amine in solution. Dichloromethane as the solvent was used all measurements in

solutions. In this research, phosgene can be produced in situ in BTA solution containing

triethylamine (TEA) upon addition of triphosgene.

Preparation of the Test Paper: Polystyrene (2 g) was dissolved in 50 mL DCM to obtain a sticky

homogenous solution and then BTA (2 mg) was added with a magnetic stir bar. A filter paper was cut

into strips, and then tied with copper wire. Then, the paper was immersed in the solution and then

taken out immediately to dry in air. Finally, the test paper with BTA was made simply to detect

oxalyl chloride and phosgene in gas phase.

Detection of oxalyl chloride and phosgene in gas phase:

Fig. S3 Schematic diagram of detection device of oxalyl chloride vapor, phosgene and other analytes vapor.

S5

Detection of oxalyl chloride vapor and phosgene in various concentrations: Various

concentration of oxalyl chloride (2*10-3

M, 1*10-2

M, 2*10-2

M and 4*10-2

M) and triphosgene

(2*10-2

M, 4*10-2

M, 6*10-2

M, 8*10-2

M and 1*10-1

M) with in DCM solutions were prepared. Using

a microliter syringes, 10 L above solutions were injected to detection devices. Specifically, 10 L

TEA (4*10-2

) in DCM solution were added into each of triphosgene vials, respectively. After 5 min,

the fluorescence of these test papers was taken pictures under 365 nm light.

Fig. S4 Fluorescence photo of BTA test papers upon the exposure to various amount of oxalyl chloride (0-20ppm,

above) and phosgene (0−50 ppm, bottom).

S6

Selective detection of oxalyl chloride vapor and phosgene over other analytes vapor.

The concentration (1*10-1

M) of DCP, SOCl2, SO2Cl2, POCl3, CH3COCl, TsCl, BsCl and BzCl were

prepared. Using a microliter syringes, 10 L above solutions were injected to detection devices

respectively. After 5 min, the fluorescence of these test papers were taken pictures under 365 nm

light.

Fig. S5 Fluorescence responses of BTA-based test papers upon exposure to oxalyl chloride (20 ppm) vapor ,

triphosgene (50 ppm) with TEA (0.01%) vapor and various other analytes vapor (100 ppm) : 0, blank; 1, oxalyl

chloride; 2, triphosgene / TEA; 3, DCP; 4, SOCl2; 5, SO2Cl2; 6, POCl3; 7, CH3COCl; 8, TsCl; 9, BsCl; 10, BzCl in

vials (20 mL) for 5 min under the irradiation of UV lamp (365 nm).

S7

EI-MS and NMR spectra of related compounds

Fig. S6 EI-MS spectra of compound 2.

Fig. S7 EI-MS spectra of compound 3.

WXJ1

m/z366 368 370 372 374 376 378 380 382 384 386 388 390 392 394 396 398 400 402 404 406 408

%

0

100

2016121502 198 (3.301) Cm (198-(170:172+228:230)) TOF MS EI+ 230383.7993

381.8017

365.8072372.7668368.9666

385.7989

386.8126

381.80

383.80

384.80

385.80

526.12

1

m/z100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700

%

0

100

2017041801 303 (5.051) Cm (303-(273+328)) TOF MS EI+ 4.29e3526.1

468.1

219.1218.7131.4

121.0188.1163.1

434.1410.0318.0289.0273.1260.1 376.1347.0

481.1

482.1

496.1

527.1

528.1

529.1

530.1 564.0 614.2

S8

Fig. S8 EI-MS spectra of BTA.

Fig. S9 EI-MS spectra of BTAH.

466.17

2

m/z120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620

%

0

100

2017041802 368 (6.134) Cm (368-(340+405)) TOF MS EI+ 6.99e3466.2

408.1

350.1

218.9129.3113.0 133.1 215.1

333.1256.0233.1

304.1287.1264.7

351.1391.1375.1

409.1 465.2

433.1

467.2

468.2

469.2

502.2 576.0552.0506.1528.1

3

m/z120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680

%

0

100

2017041803 425 (7.085) Cm (425-(395+461)) TOF MS EI+ 325520.1

219.2

216.7

130.9119.2 215.8156.2

168.9

220.1

501.7462.1414.2220.4

263.3238.0 403.0276.0315.0 346.0

445.1414.7

463.1

521.1

522.1

523.1664.0552.0

520.1

S9

Fig. S10 EI-MS spectra of BTAP.

Fig. S11 13

C NMR spectra of compound 2 (DMSO-d6).

4

m/z100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660

%

0

100

2017041804 520 (8.668) Cm (520-(484+569)) TOF MS EI+ 1.48e3492.1

376.1

375.1

219.5131.4

120.0216.0150.1 155.8

359.1342.1220.9245.0 264.4

313.1295.0

434.1

377.1433.1

378.1390.1

413.8435.1

491.9459.1

493.1

494.1

495.1

507.7 552.0

492.1

S10

Fig. S12 1H NMR spectra of compound 3 (CDCl3).

Fig. S13 13

C NMR spectra of compound 3 (DMSO-d6).

S11

Fig. S14 1H NMR spectra of BTA (DMSO-d6).

Fig. S15 13

C NMR spectra of BTA (DMSO-d6).

S12

Fig. S16 1H NMR spectra of BTAH (DMSO-d6).

Fig. S17 13

C NMR spectra of BTAH (DMSO-d6).

S13

Fig. S18 1H NMR spectra of BTAP (CDCl3).

Fig. S19 13

C NMR spectra of BTAP (DMSO-d6).

S14

Fig. S20 HR-MS spectra of BTA.

Fig. S21 HR-MS spectra of BTAH.

Fig. S22 HR-MS spectra of BTAP.

S15

References:

S1. G. A. Crosby and J. N. Demas, J. Phy. Chem., 1971, 75, 991-1024.