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1 Supplementary Material New V-shaped push-pull systems on the basis of 4,5-di(hetero)aryl substituted pyrimidines: synthesis and application for detection of nitroaromatic explosives Egor V. Verbitskiy a,b,*, Anna A. Baranova b, Kseniya I. Lugovik b, Konstantin O. Khokhlov b, Ekaterina M. Cheprakova a, Gennady L. Rusinov a,b, Oleg N. Chupakhin a,b, and Valery N. Charushin a,b a Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, S. Kovalevskoy Str., 22, Ekaterinburg, 6137, Russia b Ural Federal University, Mira St. 19, Ekaterinburg, 62, Russia Verbitsky@ios.uran.ru Dedicated to Professor Oleg G. Sinyashin on the occasion of his th anniversary Table of Contents 1. Figure S1. Fluorescence quenching studies of 6b S2 2. Figure S2. Fluorescence quenching studies of 6c S3 3. Figure S3. Solution photographs of compound 6b and 6a S4 4. Figure S4. Solution photographs of compound 6c S5 5. Figure S5. Time-resolved fluorescence emission of 6a and adduct with DNAN at different mole ratios of the analyte S6 6. Figure S6. Time-resolved fluorescence emission of 6b and adduct with DNAN at different mole ratios of the analyte S6 7. Figure S7. Time-resolved fluorescence emission of 6c and adduct with DNAN at different mole ratios of the analyte S7 8. Figure S8. The Stern Volmer plots as function of DNAN concentration in CH 3 CN, with an excitation wavelength of 3 nm for 6a solution S7 9. Figure S9. The Stern Volmer plots as function of DNAN concentration in CH 3 CN, with an excitation wavelength of 397 nm for 6b solution S8 1. Figure S1. The Stern Volmer plots as function of DNAN concentration in CH 3 CN, with an excitation wavelength of 3 nm for 6c solution S9 11. Table S1. Fluorescence life time data of pure 6a-c fluorophores at different mole ratios of DNAN S H NMR and 13 C NMR of compounds 6a-c S1 Page S1

2 (a) (b) (c) 5 (d) (e) (f) (g) 5 (h) Figure S1. Fluorescence quenching studies of 6b ( mol/l) recorded in the presence of various amounts of DNAN (a), PA (b), SA (c), TETNB (d), DNT (e), TNT (f), NB (g) and Tol (h), of which 385 nm was taken as the excitation wavelength. Page S2

3 (a) (b) (c) (d) (e) (f) (g) (h) Figure S2. Fluorescence quenching studies of 6c ( mol/l) recorded in the presence of various amounts of DNAN (a), PA (b), SA (c), TETNB (d), DNT (e), TNT (f), NB (g) and Tol (h), of which 385 nm was taken as the excitation wavelength. Page S3

(1) (2) (3) (1) (4) (5) (a) (b) Figure S3.

1-5 M) in acetonitrile (1), solution 6a with the presence of solution

1-5 M) in acetonitrile (2), solution 6b with the presence of solution

1-5 M) in acetonitrile (3), solution 6b with the presence of solution

4 (1) (2) (3) (1) (4) (5) (a) (b) Figure S3. Solution photographs of compound 6b (c = M) in acetonitrile (1), solution 6a with the presence of solution TETNB (c = M) in acetonitrile (2), solution 6b with the presence of solution DNAN (c = M) in acetonitrile (3), solution 6b with the presence of solution PA (c = M) in acetonitrile (4), solution 6b with the presence of solution SA (c = M) in acetonitrile (5): before radiation (a no emission) and during radiation (b emission, λ ex = 375 nm) at room temperature. Page S4

(1) (2) (3) (1) (4) (5) (a) (b) Figure S4.

1-5 M) in acetonitrile (2), solution 6c with the presence of solution

1-5 M) in acetonitrile (3), solution 6c with the presence of solution

5 (1) (2) (3) (1) (4) (5) (a) (b) Figure S4. Solution photographs of compound 6c (c = M) in acetonitrile (1), solution 6a with the presence of solution TETNB (c = M) in acetonitrile (2), solution 6c with the presence of solution DNAN (c = M) in acetonitrile (3), solution 6c with the presence of solution PA (c = M) in acetonitrile (4), solution 6c with the presence of solution SA (c = M) in acetonitrile (5): before radiation (a no emission) and during radiation (b emission, λ ex = 375 nm) at room temperature. Page S5

6 Intensity (a.u.) 6 4 Calculation parameters Equation A1exp(-time/TAU1)+C [Ex. Wavelength], 3. [Em. Wavelength], 557. [Number of cycles], 1 [Ex. Slit], 5 [Em. Slit], 5 6a 6a+DNAN Time ( s) Figure S5. Time-resolved fluorescence emission of 6a and adduct with DNAN at different mole ratios of the analyte. 6 5 Calculation parameters Equation A1exp(-time/TAU1)+C [Ex. Wavelength], 397. [Em. Wavelength], 535. [Number of cycles], 1 [Ex. Slit], 5 [Em. Slit], 5 6b+DNAN 6b Intensity (a.u.) Time ( s) Figure S6. Time-resolved fluorescence emission of 6b and adduct with DNAN at different mole ratios of the analyte. Page S6

7 6 5 Calculation parameters Equation A1exp(-time/TAU1)+C [Ex. Wavelength], 3. [Em. Wavelength], 512. [Number of cycles], 1 [Ex. Slit], 5 [Em. Slit], 5 6c+DNAN 6c Intensity (a.u.) Time ( s) Figure S7. Time-resolved fluorescence emission of 6c and adduct with DNAN at different mole ratios of the analyte. 1,,9,8,7,6 Model Equation Re duced Chi -Sq r ExpGro2 y = A1*exp(x/t1) + A2*exp(x/t2) + y 7,736 E-4 Adj. R-Square,98446 Value Standard Error (I/I)-1 y,1 44,42 42 (I/I)-1 A1 -,8 9,52 38 (I/I)-1 t1 -,3198,284 (I/I)-1 A2 -,357 25,59 59 (I/I)-1 t2 -,21 69,6 64 (I/I)-1 k1-3, , (I/I)-1 k2-4 6, , (I/I)-1 ta u1 -,221 67, (I/I)-1 ta u2 -,15 3, 46 DNAN ExpGro2 Fit of Sheet1 B"(I/I)-1" (I/I)-1,5,4,3,2,1,,,2,4,6,8 1, Concentrations (mm) Figure S8. The Stern Volmer plots as function of DNAN concentration in CH 3 CN, with an excitation wavelength of 3 nm for 6a solution. Page S7

8 2,5 2,25 DNAN ExpGro2 Fit of Sheet1 B"(I/I)-1" % (3,@LG) 2, 1,75 Model Equat ion ExpGro2 y = A1*exp(x/t1) + A2*exp(x/t2) + y (I/I)-1 1,5 1,25 1,,75,5,25 Reduced Chi-Sq r,295 Adj. R-Square,99387 Value Standard Error (I/I)-1 y 2,1 796,3 718 (I/I)-1 A1-1,65 162,8 155 (I/I)-1 t1 -, 14 1,1983E-4 (I/I)-1 A2 -,45 453,6 535 (I/I)-1 t2 -,4 196,1 538 (I/I)-1 k1-9, , (I/I)-1 k2-23, , (I/I)-1 tau1-7,21764e-4 8,3596E-5 (I/I)-1 tau2 -,2 98,1 66,,,1,2,3,4,5 Concentrations (mm) Figure S9. The Stern Volmer plots as function of DNAN concentration in CH 3 CN, with an excitation wavelength of 397 nm for 6b solution. Page S8

9 2, DNAN ExpGro1 Fit of Sheet1 B"(I/I)-1" 1,5 (I/I)-1 1,,5 Model Equation ExpGro1 y = A1*exp(x/t1) + y Reduced Chi-Sq,5 62 r Adj. R-Square, Value Standard Error (I/I)-1 y 1,342,7475 (I/I)-1 A1-1,2637,7999 (I/I)-1 t1 -,541,874 (I/I)-1 k -19, ,445 (I/I)-1 tau -,3494,6,,,5,1, 15,,25,3 Concentrations (mm) Figure S1. The Stern Volmer plots as function of DNAN concentration in CH 3 CN, with an excitation wavelength of 3 nm for 6c solution. Table S1. Fluorescence life time data of pure 6a-c fluorophores at different mole ratios of DNAN Mole ratio vs DNAN Fluorophore 6a (μs) Fluorophore 6b (μs) Fluorophore 6c (μs) : Page S9

10 1 H NMR (5 MHz, DMSO-d 6 ) spectrum of 6a. Page S1

11 13 C NMR (126 MHz, DMSO-d 6 ) spectrum of 6a. Page S11

12 HEM3a meg: A* ppm Page S H NMR (5 MHz, DMSO-d 6) spectrum of 6b.

13 13 C NMR (126 MHz, DMSO-d 6 ) spectrum of 6b. Page S13

14 1 H NMR (5 MHz, CDCl 3 ) spectrum of 6c. Page S14

15 VEV158c ema: A* ppm Page S C NMR (126 MHz, CDCl 3) spectrum of 6c.

General Papers ARKIVOC 2016 (iii)

General Papers ARKIVOC 2016 (iii) ew V-shaped push-pull systems based on,5-di(hetero)aryl substituted pyrimidines: their synthesis and application to the detection of nitroaromatic explosives Egor V. Verbitskiy, a,b, * Anna A. Baranova,