Supporting Information. Phthalocyanine-Porphyrin Dyads

Transcription

1 Supporting Information Ratiometric Fluorescent Detection of Pb 2+ by FRET-based Phthalocyanine-Porphyrin Dyads Dongli Zhang, Mengliang Zhu, Luyang Zhao, Jinghui Zhang, Kang Wang, Dongdong Qi, Yang Zhou, Yongzhong Bian and Jianzhuang Jiang Content 1. Chemicals and instruments, page S2. 2. Synthetic scheme of dyads 1 and 2, page S3. 3. MALDI-TOF mass spectra of dyads 1 and 2, pages S4 and S H NMR and 1 H- 1 H COSY spectra of dyads 1 and 2, pages S6-S9. 5. Fluorescence quantum yields, page S Density functional theory and Förster theory calculations, pages S11 and S Pb 2+ selectivity of dyad 2, page S Mass spectra of dyads 1 and 2 in the presence of Pb(NO 3 ) 2, page S14 9. Ratiometric fluorescent detection of Pb 2+ with dyad 1, page S References, page S16. S1

2 Chemicals and instruments. Column chromatography was conducted on silica gel ( mesh, Qingdao Ocean Chemicals) and Bio-beads ( mesh, BIORAD S-X1) with the indicated eluents. n-pentanol was freshly distilled from Na under nitrogen. 3-Porphyrinyl-phthalonitrile (3) and 4-porphyrinyl-phthalonitrile (4) were prepared according to the published procedures. [S1] All other reagents and solvents were used as received. Pb(NO 3 ) 2 3H 2 O ( 99%) was purchased from Sigma-Aldrich. AgNO 3 H 2 O, Al(ClO 4 ) 3 9H 2 O, Ba(ClO 4 ) 2 3H 2 O, CaCl 2, Cd(ClO 4 ) 2 6H 2 O, Co(ClO 4 ) 2 6H 2 O, CrCl 3, CuCl 2, FeC1 2, Fe(ClO 4 ) 3, Hg(ClO 4 ) 2, KCl, MgCl 2, MnSO 4, NaCl, NH 4 Cl, Ni(ClO 4 ) 6H 2 O and Zn(ClO 4 ) 2 6H 2 O were standard analytical reagent grade and were obtained from commercial suppliers. 1 H NMR spectra were recorded on a Bruker DPX 400 MHz spectrometer in CDCl 3 and the chemical shifts were reported relative to internal SiMe 4. MALDI-TOF mass spectra were measured on a Bruker Microflex TM LRF spectrometer with dithranol as the matrix. Elemental analyses were performed on an Elementar Vario MICRO CUBE elemental analyzer. Electronic absorption spectra were taken on a Lambda U-750 spectrophotometer. Steady-state fluorescence spectra were determined on a Hitachi F4500 fluorophotometer with excitation at 420 nm. S2

3 Scheme S1. Synthesis of the phthalocyanine-porphyrin dyads 1 and 2. S3

4 Figure S1. MALDI-TOF mass spectrum of dyad 1. S4

5 Figure S2. MALDI-TOF mass spectrum of dyad 2. S5

6 S6

7 Figure S3. 1 H NMR and 1 H- 1 H COSY spectra of dyad 1 in CDCl 3 at 293 K. * indicate the residual solvent signals. S7

8 S8

9 Figure S4. 1 H NMR and 1 H- 1 H COSY spectra of dyad 2 in CDCl 3 at 293 K. * indicate the residual solvent signals. S9

10 The method for determining fluorescence quantum yields. Fluorescence quantum yields were determined by reference to ZnTPP in benzene (Φ = 0.033) [S2] for the zinc(ii) porphyrin (ZnPor) moiety and to Pc in toluene (Φ = 0.33) [S3] according to equation S1: for the metal free phthalocyanine (H 2 Pc) moiety, Φ F x = Φ F std n x 2.A std F x 2.A x F std (S1) n std where Φ F x and Φ F std are the fluorescence quantum yields of the sample and standard respectively; F x and F std are the areas under the emission curves of the sample and standard; A x and A std are the absorbances of the sample and standard at the excitation 2 2 wavelength; and n x and n std are the refractive indices of the solvents used for the sample and standard respectively. The refractive index of the THF-MeOH binary solvent mixture (4:1 in v/v) was estimated according to the approximate equation S2: n m = n 1 v 1 + n 2 v 2 (S2) where n m is the refractive index of the binary mixture respectively; n 1 and n 2 the refractive indices of THF (1.4050) and methanol (1.3269); [S4] v 1 and v 2 are the volume fractions of THF and methanol THF-MeOH (4:1 in v/v) was calculated to be are respectively. The refractive index of S10

11 Density functional theory and Förster theory calculations The DFT calculation was carried out by M06-2X-D3 method with the basis set of 6-311G(d). [S5-S7] The center of phthalocyanine ring is determined by the average of four inner nitrogen atoms. All the calculations were carried out using Gaussian 09 program. [S8] The spectral overlap integral J DA is given by equation S3: J DA = 0 I D (λ)ε A (λ)λ 4 dλ (S3) where I D (λ) is the normalized fluorescence emission spectrum of the donor; ε A (λ) is the molar extinction coefficient of the acceptor (in dm 3 mol -1 cm -1 ) and λ is the wavelength. The orientation factor k 2 is given by equation S4: k 2 = (cos θ T 3 cos θ D cos θ A ) 2 (S4) where θ T is the angle formed by the donor absorption transition dipole and the acceptor emission transition dipole; θ D and θ A are the angles between each transition dipole and the vector joining the middle point of each dipole, respectively. The orientation angles (θ T, θ D, and θ A ) and distance between the donor and acceptor (r) are adopted from the DFT optimized molecular structures of dyads 1 and 2. S11

12 Figure S5. The DFT optimized molecular structures of dyads 1 and 2. Table S1. The DFT optimized orientation angles ( ) of dyads 1 and 2. Dyads θ T θ D θ A S12

13 Figure S6. Electronic absorption spectra (a), emission spectra (b) and ratiometric fluorescence responses (c) of dyad 2 (2 μm in THF/CH 3 OH, 4:1 in v/v, λ ex = 420 nm) upon addition of Ag +, Al 3+, Ba 2+, Ca 2+, Cd 2+, Co 2+, Cr 3+, Cu 2+, Fe 2+, Fe 3+, Hg 2+, K +, Mg 2+, Mn 2+, Na +, NH + 4, Ni 2+, Pb 2+ and Zn 2+ (20 μm), respectively. S13

14 Figure S7. MALDI-TOF mass spectra of dyads 1 and 2 in the presence of Pb(NO 3 ) 2 (10 equiv). S14

15 Figure S8. (a) Electronic absorption spectra and (b) emission spectra of dyad 1 (2 μm in THF/CH 3 OH, 4:1 in v/v, λ ex = 420 nm) upon addition of Pb 2+ (0-20 μm), the inset shows the relationship between F 605 /F 700 and Pb 2+ concentration in the range of 0-20 μm; (c) Fluorescence intensity ratio changes (F 605 /F 703 ) of dyad 1 as a rectilinear function of Pb 2+ concentration in the range of μm. S15

16 References [S1] Bian, Y.; Chen, X.; Wang, D.; Choi, C.; Zhou, Y.; Zhu, P.; Ng, D. K. P.; Jiang, J.; Weng, Y.; Li, X., Porphyrin-Appended Europium(III) Bis(phthalocyaninato) Complexes: Synthesis, Characterization, and Photophysical Properties. Chem. Eur. J. 2007, 13, [S2] Li, J.; Lindsey, J. S., Efficient Synthesis of Light-Harvesting Arrays Composed of Eight Porphyrins and One Phthalocyanine. J. Org. Chem. 1999, 64, [S3] Makarov, S.; Litwinski, C.; Ermilov, E. A.; Suvorova, O.; Röder, B.; Wöhrle, D., Synthesis and Photophysical Properties of Annulated Dinuclear and Trinuclear Phthalocyanines. Chem. Euro. J. 2006, 12, [S4] Zafarani-Moattar, M. T.; Majdan-Cegincara, R., Viscosity, Density, Speed of Sound, and Refractive Index of Binary Mixtures of Organic Solvent + Ionic Liquid, 1-Butyl-3-methylimidazolium Hexafluorophosphate at K. J. Chem. Eng Data. 2007, 52, [S5] Zhao, Y.; Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theo. Chem. Acc. 2008, 120, [S6] Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, [S7] Zhao, Y.; Truhlar, D. G. Density Functionals with Broad Applicability in Chemistry. Acc. Chem. Res. 2008, 41, [S8] Frisch, M. J. et al., Gaussian 09 D.01, Gaussian, Inc., Wallingford CT, USA, S16