A turn-off emission based chemosensor for HSO formation of a hydrogen-bonded complex

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1 SUPPLEMETARY IFRMATI (SI) A turnoff emission based chemosensor for HS 4 formation of a hydrogenbonded complex Paramjit Kaur,* a Hardeep Kaur b and Kamaljit Singh* b a Department of Chemistry, UGCCentre of Advance StudiesI, b rganic Synthesis Laboratory, Department of Applied Chemical Sciences and Technology, UGCSAP(DRSI) Department, Guru anak Dev University, Amritsar , India S1. Experimental 1. General Mass spectrum was recorded on UPLCQTF mass spectrometer. 1 H MR and 13 C MR spectra have been recorded on BRUKER Avance II 400 MHz and 100 MHz, respectively with TMS as internal standard using CD 3 D and CDCl 3 as deuterated solvent. Data are reported as follows: chemical shift in ppm (δ), integration, multiplicity (s=singlet, d=doublet, t=triplet, q=quartet, dd=double doublet), coupling constant J (Hz) and assignment. The purity of the solid products was checked by elemental analysis performed on Thermoelectron FLASH EA1112, CHS analyzer. Stock solution of 1 (1 mm) was prepared using AR grade methanol. The UVvis and fluorescence titration experiments were carried out by making dilution of the stock with methanol. Stock solution of anions (0.1M) were prepared by dissolving sodium salts of HS 4, CH 3 C, HS 3, S 2 3, S 2 4, F, Br, Cl, I, H, citrate, HC 3, C 2 3, C, H 2 P 4, HP 2 4, P 3 4, 2 and 3 in distilled water. UVvisible spectral studies were conducted on Shimadzu 1601 PC spectrophotometer with a quartz cuvette (path length, 1cm). The absorption spectra have been recorded between 1100 and 200 nm. The cell holder of the spectrophotometer was thermostatted at 25 o C for consistency in the recordings. The UVvis titration experiment was performed by adding varying concentration of HS 4 (045 μm) to 1 (30 μm) in methanol. All the absorption spectra were recorded after equilibration of solution for 5 min. The steady state fluorescence experiments were carried out on Cary Eclipse spectrofluorometer at ambient temperature. A slit width of 5 nm was used with λ ex = 320 nm and λ em = 376 nm. The titration experiment was accomplished by varying the concentration of HS 4 (060 μm) and keeping the 1

2 compound concentration constant (30µM). The working solution (30 µm) of 1 for fluorescence titration was prepared by making dilution of stock solution (1mM) with AR grade methanol. 2. Computational Methods All theoretical calculations were carried out by using the Gaussian 09 suite of programs. The molecular geometry of 1 was optimized by DFT/B3LYP 1 /6311G* method. The geometry of 1:aHS 4 was optimized by DFT/MPW1PW91/GE method in which 631G basis set was used for C and H and 6311G** basis set was used for the donor atoms (, Cl, and S). Energy values and properties of the systems were computed at the same level and considering solvent (methanol) effects by using the Cossi and Barone s CPCM (conductorlike polarizable continuum model) modification 2 of the Tomasi s PCM formalism. 3 The first 20 excited states were calculated by using timedependent density functional theory (TDDFT) calculations. The molecular orbital contours were plotted using Gauss view Chemicals Anions used in the spectrophotometric studies were added as sodium salts of analytical grade and bought from SigmaAldrich. The solvents used were also of analytical grade purchased from Thomas Baker. 4. Synthetic Procedure for 5Ethoxycarbonyl6methyl4phenyl2[(7chloroquinolin 4ylamino) butylamino] pyrimidine (1) (Scheme 1). To the stirred solution of 7chloroquinyl1,4butandiamine 4 (1.1g, 4.41 mmol) in dry THF (50ml) mixture of 5Ethoxycarbonyl6methyl2chloropyrimidines 5 (1g, 2.01mmol) and potassium carbonate (2.78g, mmol) in dry THF was added. The reaction mixture was stirred for 48hrs at room temperature. Then, the reaction mixture was filtered and THF was removed under vacuum. The residue was purified by column chromatography using MeH / EtAc as eluent to give desired product. The product was recrystallized from DCM/ Hexane. 1 L. J. Bartolottiand, and K. Fluchick, Reviews in Computational Chemistry Lipkowitz, K. B.; Boyd, B. D. Eds., VCH, ew York, 1996, 7, (a) V. Barone and M. Cossi, J. Phys. Chem. A, 1998, 102, 1995; (b) M. Cossi,. Rega, G. Scalmani, V. J. Barone, Comp. Chem., 2003, 24, S. Miertus, E. Scrocco and J. Tomasi, J. Chem. Phys. 1981, 55, 117; (b) R. Cammi, B. Mennucci and J. Tomasi, J. Phys. Chem., A 2000, 104, J. K. atarajan, J.. Alumasa, K. Yearick, K.A. EkoueKovi, L.B. Casabianca, A.C.D. Dios, C. Wolf and P.D. Roebe, J. Med. Chem., 2008, 51, (a) P. Biginelli, Gazz. Chim. Ital., 1893, 23, 360; (b) K. Singh and K. Singh, Aust. J. Chem.; 2008, 61, 910; (c) K. Singh, K. Singh, B. Wan, S. Franzblau, K. Chibale and J. Balzarini, Eur. J. Med. Chem.; 2011, 46,

3 Electronic Supplementary Material (ESI) for Analyst White solid. Rf: 0.4 (EtAc). Yield: 77%. IR (KBr): ν max / cm (H), 2986 (CH), 1708 (C=), 1268(C). Found: C, 66.10; H, 5.63;, Calc. For C 27 H Cl: C, 66.18; H, 5.72;, 14.30%. 1 H MR (400 MHz; CD 3 D; Me 4 Si; ppm) H : 0.95 (3H, t, J = 7.2 Hz, ester CH 3 ), (4H, m, CH 2 ), 2.41 (3H, s, C6CH 3 ), 3.44 (2H, t, J = 6.6 Hz, CH 2 ), 3.56 (2H, q, J = 6.6 Hz, CH 2 ), 4.04 (2H, q, J = 7.2 Hz, esterch 2 ), 6.51 (1H, d, J = 5.0 Hz, ArH), (6H, m, ArH), 7.78 (1H, d, J = 2.0 Hz, ArH), 8.08 (1H, d, J = 8.9 Hz, ArH), 8.33 (1H, d, J = 5.6 Hz, ArH). 13 C MR (75 MHz; CDCl 3 ; Me 4 Si; ppm) C : δ 13.5, 22.9, 25.8, 27.4, 40.6, 42.9, 61.1, 99.0, 115.4, 117.0, 120.8, 125.2, 127.8, 128.2, 128.7, 129.4, 134.8, 139.0, 149.0, 149.6, 151.9, 161.2, m/z (EI): (M + ). H1 BRUKER AVACE II 400 MR Spectrometer SAIF Panjab University Chandigarh H(CH 2 ) 4 H 1 Cl Current Data Parameters AME Jul EXP 10 PRC 1 F2 Acquisition Parameters Date_ Time ISTRUM spect PRBHD 5 mm PABB BB PULPRG zg30 TD SLVET MeD S 8 DS 2 SWH Hz FIDRES Hz AQ sec RG 456 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CHAEL f1 ======== UC1 1H P usec PL db SF MHz F2 Processing parameters SI SF MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC ppm avtar_saifpu@yahoo.co.in 3

4 H a b H H Cl H(CH 2 ) 4 H 2 c Cl H(CH 2 ) 4 H 1 Cl Scheme 1. Reagents and conditions (a) Pyridinium chlorochromate, CH 2 Cl 2, 24 hrs; (b) PCl 3, 105 o C, 45 minutes; (c) THF, K 2 C 3, r.t, 48 hrs. 5. Calculation of Quantum Yield Quantum yield of 1 and 1:HS 4 was calculated using formula: Φ u = Φ S I u A s /I s A u Where, Φ S is Quantum yield of standard; I u, I s are Integrated Fluorescence of standard and unknown respectively; A S, A u are absorbance of standard and unknown respectively Quinine sulphate was used as standard whose quantum yield is 0.55 in 0.1 H 2 S 4 at λ ex = 320 nm. 6 Fig. S1 ptimized structure of 1 using Gaussian 09 program (DFT/B3LYP/6311G* method; Color codes; blue:, red:, green: Cl, Grey: C, white: H). 6 Y. Li, H. Chong, X. Meng, S. Wang, M. Zhu, and Q. Guo, Dalton Trans., 2012, 41,

5 Absorbance (a.u.) Fl. Intensity (a.u.) Electronic Supplementary Material (ESI) for Analyst (a) CH 3 C, S 3 2, S 4 2, F, Br, Cl, I, H, citrate, HC 3, C 3 2 C, H 2 P 4, HP 4 2, P 4 3, 2, HS 3 90 HS Wavelength (nm) (b) HS Wavelength (nm) CH 3 C, HS 3, S 3 2, S 4 2, F, Br, Cl, I, H, citrate, HC 3, C 3 2, C, H 2 P 4, HP 4 2, P 4 3, 2, 3 Fig. S2 (a) Emission spectra ; (b) absorption spectra of 1 (30 μμ) in CH 3 H in the presence of various anions (80 μμ) in distilled H 2. 5

6 Intensity (a.u.) 1/(II 0 ) Electronic Supplementary Material (ESI) for Analyst /[HS 4 ] y = 4E07x R² = Fig. S3 Plot of 1/(II 0 ) vs 1/[HS 4 ]. Binding constant K is given by ratio of intercept to slope of graph i.e. K= Intercept/ Slope :HS 4 1:HS S 4 1:HS S 3 1:HS 4 + H 2P 4 1:HS :HS :HS 4 + F 1:HS 4 + Cl 1:HS 4 + Br 1:HS 4 + I 1:HS 4 + C [HS 4 ]/M Fig. S4 Changes in the fluorescence intensity of 1 (30 μm) in CH 3 H at 376 nm upon titration with increasing concentration of HS 4 (10, 20 and 50 μm) in distilled H 2, in the presence of other anions (60 μm) in distilled H 2. 6

7 Table S1: Standard deviation in change in fluorescence intensity in the titration of 1 (30μM) with various anions (80μM). Solution Fluorescence intensity a σ b CH 3 C HC HS HS Br Cl citrate C C H 2 P F H I HP P S S a mean fluorescence intensity at 376 nm which is determined from three repeated experiments; b standard deviation. 7

8 Absorbance (a.u.) Electronic Supplementary Material (ESI) for Analyst Wavelength(nm) Fig. S5. UV/ vis spectra of 1 (30 μm) in CH 3 H titrated with HS 4 (01.5 equiv.) in distilled H 2. Table S2: (a) Selected data of electronic transitions in 1 by TDDFT method at the B3LYP/6 311G* level. [a][b] State λ [nm (ev)] f Composition of band and CI coefficiencies (3.88) H L, 0.14; H L+1, (4.95) H L+3, 0.19; H2 L+2,0.27; H4 L+2,0.24; H4 L, 0.16; H7 L+3,0.10 [a] Calculations were carried out for the lowest 50 excited states, and only energies above 240 nm with f > 0.15 are shown. [b] f = oscillator strength; CI = configuration interaction; H = HM; L = LUM. 8

9 (b) Cartesian coordinates from the optimized structure of 1 at B3LYP/6311G* E = a.u. Center Atomic Atomic Coordinates (Å) umber umber Type X Y Z

10

11

12 (c) Frontier orbitals of 1 rbital Electron density Energy (ev) HM(H) 5.93 H H H H LUM(L)

13 L L L

14 Table S3: (a)selected data of electronic transitions in 1:aHS 4 by TDDFT method at the B3LYP/GE level. [a][b] State λ [nm (ev)] f Composition of band and CI coefficiencies (4.06) H L+1, (4.68) H1 L, 0.15; H1 L+1, 0.20; H1 L+2, 0.54; H L+2, (5.11) H5 L, 0.31; H5 L+2, 0.36; H4 L+2, 0.25; H2 L, 0.26; H2 L+2, 0.22; H1 L+2, 0.13 [a] Calculations were carried out for the lowest 20 excited states, and only energies above 240 nm with f > 0.19 are shown. [b] f = oscillator strength; CI = configuration interaction; H = HM; L = LUM. (b) Cartesian coordinates from the optimized structure of 1:aHS 4 at MPW1PW91/GE. E= a.u. Center Atomic Forces (Hartrees/Bohr) umber umber X Y Z

15

16

17

18 (c) Frontier orbitals of 1:aHS 4 rbital Electron density Energy (ev) HM (H) 6.09 H H H H

19 LUM (L) 1.38 L L

20 Complete Reference for Gaussian (Reference 10 in manuscript) Gaussian 09, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. akatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. akajima, Y. Honda,. Kitao, H. akai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. gliaro, M. Bearpark, J. J. Heyd, E. Brothers, K.. Kudin, V.. Staroverov, T. Keith, R. Kobayashi, J. ormand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi,. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,. Farkas, J. B. Foresman, J. V. rtiz, J. Cioslowski and D. J. Fox, Gaussian, Inc., Wallingford CT,