This journal is (c) The Royal Society of Chemistry 11 Highly sensitive cyanide anion detection with a coumarin-spiropyran conjugate as a fluorescent receptor Yasuhiro Shiraishi,* Shigehiro Sumiya, and Takayuki Hirai Research Center for Solar Energy Chemistry, and Division of Chemical Engineering, Graduate School of Engineering Science, saka University, Toyonaka 56-8531, Japan E-mail: shiraish@cheng.es.osaka-u.ac.jp Electronic Supplementary Information (ESI ) Contents page Experimental procedure... Synthesis... Nonlinear fitting of the fluorescence titration data... 3 Calculation details... 4 Table S1. Electronic transition properties of and CN..... 5 Fig. S1 1 H NMR chart of... 6 Fig. S 13 C NMR chart of... 7 Fig. S3 EI-MS chart of... 8 Fig. S4 Change in absorption spectra of under 334 nm irradiation... 9 Fig. S5 Change in absorption spectra of under 55 or 38 nm irradiation... 1 Fig. S6 Effect of other anions on the fluorescence response of to CN... 11 Fig. S7 Change in fluorescence spectra of upon CN addition.. 1 Fig. S8 Absorption titration of with CN... 1 Fig. S9 ESI-MS chart of measured with CN... 13 Fig. S1 Fluorescence titration of with CN... 14 Fig. S11 Absorption and fluorescence spectra of 7-hydroxy-4-methylcoumarin... 14 Fig. S1 Fluorescence decays of 7-hydroxy-4-methylcoumarin and CN... 15 Cartesian coordinates of (MC) and CN... 16 1S
This journal is (c) The Royal Society of Chemistry 11 Experimental procedure Absorption spectra were measured on an UV-visible photodiode-array spectrophotometer (Shimadzu; Multispec-15) equipped with a temperature controller S-17. [1] Fluorescence spectra were measured on a JASC FP-65 fluorescence spectrophotometer. Time-resolved emission decay analysis was carried out on a PTI-3 apparatus (Photon Technology International) using a Xe nanoflash lamp filled with N. [] Light irradiations were carried out with a Xe lamp (3 W; Asahi Spectra Co. Ltd.; MAX-3) equipped with 334 nm (light intensity: 69.1 mw m ), 38 nm (53.8 mw m ), and 55 nm (3.5 mw m ) band-pass filters, respectively. 1 H and 13 C NMR spectra were obtained by a JEL JNM-GSX7 Excalibur and JNM-AL4 spectrometer. EI- and ESI-MS analysis was performed by a JEL JMS 7 Mass Spectrometer. Synthesis Compound (1,3,3,4 -tetramethylspiro[indoline-,8 -H,8H-pyrano[,3-h]chromen--one]) N + H CH MeH reflux, 3 h N (66%) 1,3,3-Trimethyl--methylideneindole (161 mg,.93 mmol) and 8-formyl-7-hydroxy-4- methylcoumarin ( mg,.98 mmol) [3] were refluxed in MeH (5 ml) for 3 h under N. The resultant was concentrated by evaporation. The crude product was purified by silica gel column chromatography with CH Cl, affording as a white solid. Yield: mg, 66 %. 1 H NMR (7 MHz, acetone-d 6, TMS): δ = 7.53 (d, J = 8.7 Hz, 1H, ArH), 7.4 (d, J = 1.6 Hz, 1H, CCHCH ), 7.18 7.11 (m, H, ArH), 6.8 (t, J = 7.4 Hz, 1H, ArH), 6.68 (d, J = 8.7 Hz, 1H, ArH), 6.6 (d, J = 7.6 Hz, 1H, ArH), 6.14 (d, J = 1. Hz, 1H, CCHCCH 3 ), 5.96 (d, J = 1.6 Hz, 1H, CCHCH ),.8 (s, 3H, NCH 3 ),.4 (d, J = 1. Hz, 3H, CCHCCH 3 ), 1.3 (s, 3H, C(CH 3 ) ), 1.19 ppm (s, 3H, C(CH 3 ) ); 13 C NMR (68 MHz, CDCl 3, TMS): δ = 16.6, 157., 15.7, 149.6, 147.7, 136., 17.5, 14.9, 1.4, 11.3, 119.5, 119.3, 11.8, 111.7, 111.3, 17.1, 16.8, 15.4, 5., 8.8, 5.8,., 18.7 ppm; EI-MS: m/z: calcd for C 3 H 1 N 3 : 359.; found: 359.1 [M + ]; HRMS (EI + ): m/z: calcd for C 3 H 1 N 3 [M + ]: 359.151; found: 359.153. S
This journal is (c) The Royal Society of Chemistry 11 Nonlinear fitting of the fluorescence titration data [4] When assuming a 1:1 stoichiometry for interaction between and CN, the equilibrium is given by the following equation: K + CN ass CN (1) The association constant, K ass, is expressed as: K [ CN ] [ CN ] ass = = [ ][ CN ] ([ ] -[ CN ])([ CN ] -[ CN ]) () [ CN ], [], and [CN ] are the equilibrium concentrations of the CN species, free, and free CN, respectively. [] and [CN ] are the initial concentrations of and CN, respectively. The eq. is transformed to: [ CN ([ ] ] = + [ CN ] + 1 1 ) ([ ] + [ CN ] + ) 4[ ] [ CN ] K - ass Kass (3) Fluorescence intensity is given as follows: [5] λ I =Φ [ ] (4) λ λ I = Φ [ ] +Φ [ CN ] (5) CN I (6) λ λ max = Φ [ ] max+φ [ CN ] CN max I is the intensity of at 453 nm without anion under UV irradiation, I is the intensity of at 453 nm obtained with CN under UV irradiation, and I max is the intensity of at 453 nm in the presence of excess amount of CN under UV irradiation. Φ λ and Φ λ CN- are the fluorescence quantum yields for and CN. By means of eqs 4, 5 and 6, the following equation is obtained: I max I I I = [ max CN ] [ CN ] (7) With excess amount of CN, [. CN ] max is almost equal to []. The eq 7 can therefore be replaced as follows: I max I I I [ ] = [ CN ] (8) From eq. 3 and 8, the following equation is obtained: 3S
This journal is (c) The Royal Society of Chemistry 11 I max I 1 {([ ] [ ] ) ([ ] [ ] 1 I = I + + CN + - + CN + ) 4[ ] [ CN ] } (9) [ ] K ass K ass The eq. 9 was used for fitting of the fluorescence titration data with CN. Calculation details Preliminary geometry optimizations were performed using the WinMPAC version 3. software (Fujitsu Inc.) at the semiempirical PM3 level. [6] The obtained structures were fully refined with tight convergence criteria at the DFT level with the Gaussian 3 package, [7] using the B3LYP/6-31G* basis set for all atoms. The excitation energies and the oscillator strength of each structure were calculated by the time-dependent density-functional response theory (TD-DFT) [8] at the same level of optimization using the polarizable continuum model (PCM) [9] with water as a solvent. Cartesian coordinates for the MC form of and CN species are summarized in the end of this ESI. [1] Y. Shiraishi, R. Miyamoto, T. Hirai, Langmuir 8, 4, 473 479. [] Y. Shiraishi, Y. Tokitoh, T. Hirai, rg. Lett. 6, 8, 3841 3844. [3] D. R. Bender, D. Kanne, J. D. Frazier, H. Rapoport, J. rg. Chem. 1983, 48, 79 719. [4] J. Bourson, J. Pouget, B. Valeur, J. Phys. Chem. 1993, 97, 455 4557. [5] R. Yang, K. Li, K. Wang, F. Zhao, N. Li, F. Liu, Anal. Chem. 3, 75, 61 61. [6] Y. Shiraishi, N. Saito, T. Hirai J. Am. Chem. Soc. 5, 17, 834 836. [7] a) Gaussian 3, Revision B.5, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, Jr., J. A. Montgomery, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, 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, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain,. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. rtiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 4. b) GaussView, Version 3.9, R. Dennington II, T. Keith, J. Millam, K. Eppinnett, W. L. Hovell, R. Gilliland, Semichem, Inc., Shawnee Mission, KS, 3. [8] R. E. Stratmann, G. E. Scuseria, M. J. Frisch, J. Chem. Phys. 1998, 19, 818 84. [9] M. Cossi, V. Barone, R. Cammi, J. Tomasi, Chem. Phys. Lett. 1996, 55, 37 335. 4S
This journal is (c) The Royal Society of Chemistry 11 Table S1. Calculated excitation energy (E), wavelength (λ), ground to excited state transition electric dipole moments (µ) and oscillator strength (f) for low-laying singlet state (S n ) of the MC form of and CN. (MC) S S 1 Main orbital transition (CIC a ) HM 1 LUM (.1) HM LUM (.6) S S HM LUM (.69) S S 3 HM 1 LUM (.66) CN S S 1 S S S S 3 HM LUM (.13) HM LUM (.61) HM LUM+1 (.19) HM LUM (.17) HM LUM+1 (.64) HM 3 LUM (.4) HM LUM (.11) HM 1 LUM (.63) E (ev) [λ (nm)].479 [51.67] 3.664 [44.33] 3.1169 [397.78] 3.61 [38.7] 3.5144 [35.78] 3.8167 [34.85] a CI expansion coefficients for the main orbital transitions. µ (Debye) µ x µ y µ z µ tot 3.15.61. 3..6138...1...9.19..3.48. 1.61.8 1.6.17 1.95.4.19..3458.3.55.1.6.95 f 5S
This journal is (c) The Royal Society of Chemistry 11 N Fig. S1 1 H NMR chart of (acetone-d 6, 7 MHz). 6S
This journal is (c) The Royal Society of Chemistry 11 N Fig. S 13 C NMR chart of (CDCl 3, 68 MHz). 7S
This journal is (c) The Royal Society of Chemistry 11 N Fig. S3 EI-MS chart of. 8S
This journal is (c) The Royal Society of Chemistry 11 a).3 5 min. A.1 b).3 min 3 4 5 6 37 nm A. 58 nm.1 1 3 4 5 t / min Fig. S4 (a) Time-dependent change in absorption spectra of (1 µm) measured in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under UV irradiation (334 nm) at 5 C. (b) Change in absorbance of 37 and 58 nm bands. 9S
This journal is (c) The Royal Society of Chemistry 11 a) A.3 min..1 A.3. 37 nm.1 58 nm 1 3 4 5 6 7 7 min t / min 3 4 5 6 b) A.3..1 min A.3. 37 nm.1 58 nm 1 3 4 5 6 7 t / min 7 min 3 4 5 6 Fig. S5 Time-dependent change in absorption spectra of (1 µm) measured in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under irradiation of (a) 38 nm and (b) 55 nm monochromatic light at 5 C. The measurements were carried out as follows: UV light (334 nm) was irradiated to the solution containing for 3 min. The spectral measurements were then started under irradiation of the respective monochromatic light. (Inset) Change in absorbance of 37 and 58 nm bands. 1S
This journal is (c) The Royal Society of Chemistry 11 a) 5 + CN - or + CN - + other anions 15 5 Fl 453 nm 15 1 5 CN - + F - Fl 1 5 4 45 5 55 6 b) CN - + Cl - CN - + Br - CN - + I - CN - + Ac - CN - + H P 4 - CN - + HS 4 - CN - + Cl 4 - CN - + N 3 - CN - + SCN - CN - Fig. S6 (a) Fluorescence spectra (λ ex = 39 nm) of (1 µm) measured with 5 equiv of CN together with 5 equiv of other respective anions in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under UV irradiation (334 nm) at 5 C. The fluorescence measurements were carried out after the solution was stirred for 3 min under UV irradiation. (b) Fluorescence intensity of the respective solutions. 11S
This journal is (c) The Royal Society of Chemistry 11 a) b) 5 5 5 FI 15 1 45 min FI 453 nm 15 1 5 1 3 4 t / min FI 15 1 45 min FI 453 nm 5 15 1 5 1 3 4 t / min 5 5 4 45 5 55 6 4 45 5 55 6 Fig. S7 Time-dependent change in the fluorescence spectra (λ ex = 39 nm) of (1 µm) measured after addition of (a) 1 equiv or (b) 5 equiv of CN in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under UV irradiation (334 nm) at 5 C. (Inset) Change in fluorescence intensity at 453 nm..3 A.3..1 [CN - ] µm A..1 4 6 8 1 [CN - ] / [] 1 µm 37 nm 58 nm 3 4 5 6 Fig. S8 Absorption titration of (1 µm) with CN in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under UV irradiation (334 nm) at 5 C. Each spectrum was obtained after stirring the solution for 3 min with UV irradiation. (Inset) Change in absorbance of 37 and 58 nm bands. 1S
This journal is (c) The Royal Society of Chemistry 11 [ + CN + n-bu 4 N + ] + m/z 869.7 (Calculated:[ + CN + n-bu 4 N + ] + m/z 869.7) Fig. S9 ESI-MS chart of a MeCN solution containing of and equiv of n-bu 4 N + salt of CN obtained after UV irradiation (334 nm). 13S
This journal is (c) The Royal Society of Chemistry 11 Fl 5 4 3 [CN - ] 5 µm Fl 1 8 6 4 [CN - ] 1 µm.5 µm µm 4 45 5 55 6 1 4 45 5 55 6 Fig. S1 Change in fluorescence spectra (λ ex = 37 nm) of (1 µm) during titration with CN in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under UV irradiation (334 nm) at 5 C. The spectra at each CN concentration were obtained after stirring the solution for 3 min under UV irradiation. The blue and red spectra were obtained with and.5 µm CN. A) 1. a b A (normalized).8.4 B) FI (normalized) 1..8.4 3 4 5 6 a b 4 45 5 55 6 Fig. S11 (A) Absorption spectra of (a) 7-hydroxy-4-methylcoumarin (1 µm) in a water/mecn mixture (8/ v/v; ph 1.8) and (b) (1 µm) measured with 5 equiv of CN in a water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) under UV irradiation (334 nm) at 5 ºC. (B) Normalized fluorescence spectra of (a) 7-hydroxy-4-methylcoumarin (λ ex = 3 nm) and (b) (λ ex = 39 nm) with 5 equiv of CN under UV irradiation at 5 ºC. The spectrum (b) was obtained after stirring the solution for 3 min under UV irradiation. 14S
This journal is (c) The Royal Society of Chemistry 11 a) 1 Intensity A.C. 1 1 5 1 15 t / ns W.R. species 7-hydroxy-4-methylcoumarin τ / ns (a / %) 4.1 (1) χ 1.59 b) 1 Intensity 1 1 A.C. 5 1 15 t / ns W.R. N CN τ / ns species (a / %) 4.1 CN - (1) χ 1.7 Fig. S1 (a) Fluorescence decay of 7-hydroxy-4-methylcoumarin in a water/mecn mixture (8/ v/v; ph 1.8) (λ ex = 337 nm, λ em = 448 nm). (b) Fluorescence decay of measured with 5 equiv of CN in a buffered water/mecn mixture (8/ v/v; CHES 1 mm, ph 9.3) (λ ex = 337 nm, λ em = 453 nm). The measurement was carried out after stirring the solution for 3 min under UV irradiation (334 nm). Shown as insert are the decay times (τ / ns) and the normalized pre-exponential factors (a). For judging the quality of the fit, chi-squares (χ ), autocorrelation functions (A.C.), and weighted residuals are also shown. 15S
This journal is (c) The Royal Society of Chemistry 11 Cartesian Coordinates (in Å) of the MC form of N (MC) C -6.45141.84195.83 C 4.997946 -.958784.151 C -6.48171-1.9789 -.54.38413-3.44347.146 C -4.958498-1.84753 -.7 C 6.4988 -.811588.311 C -3.885766 -.95631 -.19 H -7.461314.48759.474 C -4.749.4341.41 H -7.183-1.967847 -.156 C -5.35635.959396.41 H -4.818863 -.916714 -.553 N -.5347-1.5194 -.367 H -5.516331.3457.66 C -1.76149 -.765 -.54 H.94176-1.919 -.33 C -.718543 1.1875.4 H -.9994 1.99773 -.31 C -.37556 -.117164 -.35 H 5.7348 1.78894.141 C.453979 1.1596 -.186 H 4.3139 3.657319 -.131 C 1.844796 1.118876 -.198 H -1.587478.496377 1.3384 C.7747.9384 -.19 H -.654695 1.3895.178669 C 4.155544.983.17 H -3.338797.758496 1.9967 C 4.65574 1.5668.17 H -1.587939.496937-1.3358 C 3.83859.64567 -.115 H -3.339311.758671-1.989 C.383468.513374 -.68 H -.6555 1.381483 -.17834 C -.556693 1.998 1.75864 H -1.9939 -.7191 -.887599 C -.5574 1.99353-1.753 H -.71499-3.3131 -.158 C -1.9388 -.5675 -.451 H -1.391 -.711175.887666 1.63858 3.53675 -.441 H 5.336-3.1494.37.4195-1.17786 -.11 H 6.98798-1.789169.198 C 3.5578 -.41978.116 H 6.84589 -.58144.884 C 4.4385 -.383.197 H 6.84768 -.57848 -.881539 16S
This journal is (c) The Royal Society of Chemistry 11 Cartesian Coordinates (in Å) of the CN species N CN CN C -4.3687 -.7878.813799 1.759-3.19117 -.81694 C -4.5641 -.113148.3377 C 5.87564-1.956937.1111 C -3.76469 -.87876.15144 C -1.99738.49596 -.945681 C -3.51958 -.186113 1.8788 N -.989 3.56465-1.39399 C -3.665 -.861736 -.5198 H -4.69694-3.865.745644 C -3.716496 -.15743 -.36458 H -4.648577 -.6119.91854 N -.733781 1.9956.87991 H -3.761 -.3319 3.11355 C -1.98891 1.134545 -.378374 H -3.685136 -.67964-1.77576 C -.685883.7313-1.9866 H -.36366 -.37881.9975 C -.47511.75896 -.178 H.43817.61443 -.738 C.5998 1.553591 -.11148 H 5.847658.65515.6941 C 1.994787 1.41489.11789 H 4.96448.937771.8564 C.561896 -.3757.7889 H -3.555893 1.43563 -.7993 C 3.9488 -.9333.181188 H -4.5636 1.745-1.31499 C 4.7878.84743.48766 H -4.49376 -.5 -.49697 C 4.8138.9735.583349 H -1.34716.1485 -.994668 C.8671.3977.398877 H -.3757-1.79355 -.96468 C -3.888356.7877 -.18383 H -.96976-1.1831-1.878983 C -1.775585 -.61964 -.334776 H -1.93337.818936 1.736 C -.53444 1.84173.4895 H -1.414454 1.3473.54854.431951 3.561671.4891 H -3.77847 1.94843.75371 1.71868-1.76 -.3537 H 3.8665-3.6665 -.43838 C.1343 -.388876 -.51974 H 6.58583-3.57.6381 C 3.53183 -.637476 -.3487 H 6.1963-1.68671 1.16617 C 4.411579-1.6368.78 H 6.5746-1.48 -.5384 17S