This journal is The Royal Society of Chemistry 212 Supporting Information Novel pyrene- and anthracene-based Schiff base derivatives as Cu 2+ and Fe 3+ fluorescence turn-on sensors and for aggregation induced emissions Muthaiah Shellaiah, Yen-Hsing Wu, Ashutosh Singh, Mandapati V. Ramakrishnam Raju and Hong-Cheu Lin* *Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu 349, Taiwan (ROC) linhc@mail.nctu.edu.tw Table of contents: Experimental section (S1) General information (S1) Synthesis of F1 and F2 (S1-S2) 1 H NMR, 13 C NMR and Mass (FAB) Scanned spectra of P1 and A1 (S3-S5) Absorbance spectra and stoichiometries of sensor responses of P1 and A1 (S6-S7) Detection limit (LOD) calculations and sensor reversibilities of P1 and A1 with Cu 2+ and Fe 3+ ions, respectively. (S8-S9) P1+Cu 2+ and A1+Fe 3+ sensor responses as a function of phs and PL spectra of P1 and A1 towards ph solutions (S1-S11) Determination of association constants of sensor responses of P1 and A1 (S12) Time dependent sensor responses of P1 and A1 (S13) Counter ions effect on sensor responses (S14) Absorbance spectra, quantum yield (Φ) changes of P1 and A1, upon increasing the concentrations of water (-9%) as a function of time (S14-S16) Time resolved fluorescence spectra (TRPL) of P1 in CH 3 CN (% and 8% of water) and A1 in THF (% and 6% of water) measured after 18 hours (S17) TRPL decay constants of P1 and A1 (Table S1) (S18) Notes and References (S18)
This journal is The Royal Society of Chemistry 212 General Information Experimental Section All anhydrous reactions were carried out by standard procedures under nitrogen atmosphere to avoid moisture. The solvents were dried by distillation over appropriate drying agents. Reactions were monitored by TLC plates and column chromatography was generally performed on silica gel. 1 H and 13 C NMR were recorded on a 3 MHz spectrometer. The chemical shifts (δ) are reported in ppm and coupling constants (J) in Hz and relative to TMS (.) for 1 H and 13 C NMR, (s, d, t, q, m, and dd means single, double, ternary, quadruple, multiple, and doublet of doublet, respectively), and d-chloroform (7.26) & (77.), d-thf (3.58) & (66.6) was used as references for 1 H and 13 C NMR, respectively. Mass spectra (FAB) were obtained on the respective mass spectrometer. Elemental analysis was carried out by Elemental Vario EL. Absorption and fluorescence spectra were measured on V-67 Spectrophotometer and F-45 Fluorescence Spectrophotometer, respectively. Identification and purity of the compounds P1 and A1 were characterized by NMR ( 1 H & 13 C), and Mass (FAB). Time-resolved photoluminescence (TRPL) spectra were measured using a home-built single photon counting system. Excitation was performed using a 45 and 5 nm diode laser (Picoquant PDL-2, 5 ps fwhm, 2 MHz). The signals collected at the excitonic emissions of solutions were connected to a time-correlated single photon counting card (TCSPC, Picoquant Timeharp 2). The emission decay data were analyzed with the biexponential kinetics in which two decay components were derived. The lifetime values (τ 1 and τ 2 ) and pre-exponential factors (A 1 and A 2 ) were determined and summarized. -14 ph buffers were freshly prepared as per the literature. 1 Sensor titrations Compounds P1 and A1 were dissolved in CH 3 CN and THF at 1 x 1-5 M concentration. Li +, Ag +, K +, Na +, Cs +, Ni 2+, Fe 3+, Co 2+, Zn 2+, Cd 2+, Pb 2+, Ca 2+, Cr 3+, Mg 2+, Cu 2+, Mn 2+, Hg 2+, Fe 2+, and Ag 2+ metal cations were dissolved in water medium at 1x1-3 M concentration from their respective chloro compounds. 5% Pent methyl diethylene triamine (PMDTA) was dissolved in CH 3 CN and THF, respectively for sensor reversibilities. For counter ion effect on Cu 2+ and Fe 3+ sensors responses Cu (OAc) 2, Cu(NO 3 ) 2, CuCl 2, CuBr 2, Cu (ClO 4 ) 2, Cu (IO 3 ) 2 and CuSO 4 and K 3 [Fe (CN) 6 ], Fe(NO 3 ) 3, FeCl 3, FeF 3, Fe (OH) 3, Fe (ClO 4 ) 3, Fe (IO 3 ) 3 and Fe 2 (SO 4 ) 3 were dissolved in water medium at 1x1-3 M concentration. However, Cu (OH) 2 was dissolved in NH 4 OH medium at 1x1-3 M concentration. General procedure 2, 3 for the synthesis of compounds P1 and A1 To 1 equiv. of aromatic amine derivatives in 5 ml of methanol, 1 equiv. of aromatic aldehyde derivatives were added with constant stirring under nitrogen and then refluxed for 12 hrs. The reaction was monitored by TLC, after completion, the reaction mixture was cooled and the solvent was evaporated to give the crude product, which was recrystallized from ethanol to afford pure compounds (P1 and A1). 2-(pyren-1-ylmethyleneamino)phenol (P1): Bright yellow solid; 98% yield; 1 H NMR (3 MHz, CDCl 3 ) δ: 6.95 6.99 (t, J = 6. Hz, 1H), 7.3 (d, J = 6., 1H), 7.7 7.13 (d, J = 9. Hz, 1H), 7.25 7.5 (m, 2H), 7.96 8.16 (m, 7H), 8.66 8.71 (dd, J = 7.5 Hz, 2H), 9.6 (s, 1H (-OH)); 13 C NMR (3 MHz, CDCl 3 ) δ: 115.4, 115.98, 12.2, 121.63, 123.41, 125.77, 125.95, 126.3, S1
This journal is The Royal Society of Chemistry 212 127.19, 128.53, 129.28, 133.41, 136.51, 152.38, 155.1; FAB: m/z = 321 (M +, 1%). Anal. Calcd for C 23 H 15 NO: C, 85.96; H, 4.7; N, 4.36. Found: C, 85.54; H, 4.68; N, 4.35. 2-((anthracen-2-ylimino)methyl)phenol (A1): Pale-yellow solids; 71% yield; 1 H NMR (3 MHz, d-thf) δ: 6.95 7.3 (t, J = 12 Hz, 2H), 7.7 (d, J = 9. Hz, 1H), 7.96 8.27 (m, 8H), 8.71 (s, 1H), 9.13-9.29 (m, 2H), 12.96 (s, 1H (-OH)); 13 C NMR (3 MHz, CDCl 3 ) δ: 116.6, 118.35, 12.63, 123.41, 125.95, 126.3, 126.94, 127.19, 128.53, 129.28, 13.91, 131.6, 134.41, 138.91, 154.17, 156.59; FAB: m/z = 297 (M +, 1%). Anal. Calcd for C 21 H 15 NO: C, 84.82; H, 5.8; N, 4.71. Found: C, 84.5; H, 5.7; N, 4.73. S2
This journal is The Royal Society of Chemistry 212 N HO P1 Fig. S1 1 H NMR spectrum of P1 in d-chloroform. N HO P1 Fig. S2 13 C NMR spectrum of P1 in d-chloroform. S3
This journal is The Royal Society of Chemistry 212 N HO P1 Fig. S3 Mass (FAB) spectrum of P1. N A1 HO Fig. S4 1 H NMR spectrum of A1 in d-thf. S4
This journal is The Royal Society of Chemistry 212 N A1 HO Fig. S5 13 C NMR spectrum of A1 in d-thf. N A1 HO Fig. S6 Mass (FAB) spectrum of A1. S5
This journal is The Royal Society of Chemistry 212 1.4 1.2 1. Absorbance/A.U..8.6.4 3 M.2. 3 35 4 45 5 Wavelength/nm.85.9.95 1. A 395 1.5 1.1 1.15 1.2 1.25..1.2.3.4.5.6 XM Fig. S7 Absorbance spectral changes of P1 (1x1-5 M) in CH 3 CN, titrated with -3 μm (with an equal span of 3 μm) of Cu 2+ ions in H 2 O and stoichiometry calculations based on absorbance changes at 395 nm; X M = [Cu 2+ ] / [Cu 2+ ] + [P1]; where X M = mole fraction, [Cu 2+ ] and [P1] are concentrations of Cu 2+ and P1; P1+Cu 2+ = 2:1 stoichiometry (ca..412). S6
This journal is The Royal Society of Chemistry 212 3 Absorbance/A.U. 2 1 3 M 3 35 4 45 5 Wavelength/nm 2.54 2.56 A 346 2.58 2.6 2.62..1.2.3.4.5.6 X M Fig. S8 Absorbance spectral changes of A1 (1x1-5 M) in THF, titrated with -3 μm (with an equal span of 3 μm) of Cu 2+ ions in H 2 O and stoichiometry calculations based on absorbance changes at 395 nm; X M = [Fe 3+ ] / [Fe 3+ ] + [A1]; where X M = mole fraction, [Cu 3+ ] and [A1] are concentrations of Cu 2+ and A1; A1+Fe 3+ = 2:1 stoichiometry (ca..37). S7
This journal is The Royal Society of Chemistry 212 6 5 4 y = 11.47859 +.4867x R 2 =.9845 I/I 3 2 1 LOD = 9.72 x 1-7 1 2 3 4 5 6 [Cu 2+ ]/ M 4 35 3 25 y =.6962 +.236x R 2 =.98518 I/I 2 15 1 5 LOD = 2.95 x 1-6 1 2 3 4 5 6 [Fe 3+ ]/ M Fig. S9 Standard deviations and linear fitting for detection limit calculations of P1 + Cu 2+ and A1 + Fe 2+. [Note: Detection limit calculations were based on relative fluorescence intensity changes versus respective metal ion concentrations]. S8
This journal is The Royal Society of Chemistry 212 Fluorescence intensity/a.u. 1 8 6 4 2 P1 P1 + Cu 2+ + PMDTA (5%) P1 + Cu 2+ Fluorescence intensity/a.u. 1 8 6 4 2 A1 A1 + Fe 3+ + PMDTA (5%) A1 + Fe 3+ 4 45 5 55 6 Wavelength/nm 4 45 5 55 6 65 Wavelength/nm 12 1 P1 + Cu 2+ + PMDTA (c) 1 A1 + Fe 3+ + PMDTA (d) 8 PL intensity/a.u. 8 6 4 2 PL intensity/a.u. 6 4 2 + Cu 2+ 1 2 3 4 Cycles + Fe 3+ 1 2 3 4 Cycles Fig. S1 Sensor reversibilities and reversible cycles of (a, c) P1 + Cu 2+ and (b, d) A1 + Fe 3+. S9
This journal is The Royal Society of Chemistry 212 65 6 55 I/I 5 45 4 2 4 6 8 1 12 14 ph 4 35 3 I/I 25 2 15 1 2 4 6 8 1 12 14 ph Fig. S11 Sensor responses of P1 + Cu 2+ and A1 + Fe 3+, as a function of phs (-14). S1
This journal is The Royal Society of Chemistry 212 Fluorescence intensity/a.u. 1 ph= ph=1 ph=2 8 ph=3 ph=4 ph=5 6 ph=6 ph=7 ph=8 ph=9 4 ph=1 ph=11 ph=12 2 ph=13 ph=14 4 45 5 55 6 65 W avelength/nm Fluorescence intensity/a.u. 6 55 5 45 4 35 3 25 2 15 1 5 ph= ph=1 ph=2 ph=3 ph=4 ph=5 ph=6 ph=7 ph=8 ph=9 ph=1 ph=11 ph=12 ph=13 ph=14 4 45 5 55 6 65 wavelength/nm Fig. S12 PL spectral changes of P1 (2 μm) in CH 3 CN and A1 (2 μm) in THF upon the addition of 1 μm of ph (-14) buffers in H 2 O. S11
This journal is The Royal Society of Chemistry 212 Determination of Association Constant: 4, 5 Assuming a 2:1 complex formation, the association constant was calculated on the basis of the titration curves of the sensor P1 and A1 with Cu 2+ and Fe 3+. Association constants were determined by a linear least square fitting of data with the following equation as a referenced method. [Cu 2+ ] = 1/2K a [L] T. x/(1-x 2 ) + [L] T /2. x and [Fe 3+ ] = 1/3K a [L] T. x/(1-x 3 ) + [L] T /3. x Where K a is complex association constant; [Cu 2+ ] and [Fe 3+ ] are the concentrations of Cu 2+ and Fe 2+ ions; [L] T is the initial concentration of sample; x=i-i/imax-i; I, I and I is the absorption intensity at 455 nm (P1) or 495 nm (A1) of respective species, free ligand and the absorption intensity at 455 nm (P1) or 495 nm (A1) upon the addition of Cu 2+ and Fe 3+, respectively. I-I / I max -I 1.2 1..8.6.4 R 2 =.9861 K a = 1.96 x 1 6 M -1.2. 1 2 3 4 5 6 [Cu 2+ ]/M 1. I-I / I max -I.8.6.4 R 2 =.98885 K a = 1.88 x 1 5 M -1.2. 1 2 3 4 5 6 [Fe 3+ ]/M Fig. S13 Determination of association constants of P1+Cu 2+ and A1+Fe 3+ based on linear least square fitting. S12
This journal is The Royal Society of Chemistry 212 1 1 minutes 1 1 minutes PL intensity/a.u. 8 6 4 2 PL Intensity/A.U. 8 6 4 2 4 45 5 55 Wavelength/nm 45 5 55 6 Wavelength/nm 6 5 (c) 4 35 3 (d) 4 25 I/I 3 2 1 I/I 2 15 1 5 2 4 6 8 1 Time/minutes 2 4 6 8 1 Time/minutes Fig. S14 Time dependent fluorescence spectral changes of P1 (2 μm) in CH 3 CN (λ ex = 395 nm) with 1 μm Cu 2+ in H 2 O and A1 (2 μm) in THF (λ ex = 395 nm) with 1 μm Fe 3+ in H 2 O (each measurement carried out at equal span of 2 seconds). (c and d) relative fluorescence intensity changes of P1 and A1, respectively, as a function of time (-1 min.). S13
This journal is The Royal Society of Chemistry 212 PL Intensity/A.U. 12 1 8 6 4 2 P1 OH - NO 3 - IO 3 - Br - SO 4 2- ClO 4 - Cl - CH 3 COO - 4 45 5 55 6 Wavelength/nm PL Intensity/A.U. 12 1 8 6 4 2 A1 CN - NO 3 - SO 4 2- ClO 4 - IO 3 - F - Cl - OH - 45 5 55 6 65 Wavelength/nm Fig. S15 Sensor responses of P1 and A1 towards Cu 2+ and Fe 3+ in presence of different counter ions ( for Cu 2+ sensors CH 3 COO -, NO 3 -, Cl -, Br -, OH -, ClO 4 -, IO 3 - and SO 4 2- and for Fe 3+ sensors CN -, NO 3 -, Cl -, F -, OH -, ClO 4 -, IO 3 - and SO 4 2- were taken as counter ions) S14
This journal is The Royal Society of Chemistry 212 Absorbance/A.U..3.2 9% (Water) P1 (%) P1 (1%) P1 (2%) P1 (3%) P1 (4%) P1 (5%) P1 (6%) P1 (7%) P1 (8%) P1 (9%).1. 3 4 5 W avelength/nm Absorbance/A.U..6.5.4.3.2 9% (Water) A1 (%) A1 (1%) A1 (2%) A1 (3%) A1 (4%) A1 (5%) A1 (6%) A1 (7%) A1 (8%) A1 (9%).1. 3 4 5 W avelength/nm Fig. S16 Absorbance spectral changes of P1 and A1, upon increasing the concentration of water (-9%) (Note: the spectra were taken after 18 hours). S15
This journal is The Royal Society of Chemistry 212.8.7.6.5.4.3 P1(%) P1(1%) P1(2%) P1(3%) P1(4%) P1(5%) P1(6%) P1(7%) P1(8%) P1(9%).2.1. 2 4 6 8 1 12 14 16 18 2 Time/hours.7.6.5.4.3 A1(%) A1(1%) A1(2%) A1(3%) A1(4%) A1(5%) A1(6%) A1(7%) A1(8%) A1(9%).2.1. 2 4 6 8 1 12 14 16 18 2 Time/hours Fig. S17 Quantum yield (Φ) changes of P1 and A1, upon increasing the concentration of water (-9%) as a function of time (-18 hours). S16
This journal is The Royal Society of Chemistry 212 1 PL intensity/a.u. 8 6 4 P1 (%) P1 (8%) 2 4 45 5 55 6 65 7 75 Delaytime/ns 1 PL intensity/a.u. 8 6 4 A1 (%) A1 (6%) 2 3 4 5 6 7 8 9 1 11 12 delaytime/ns Fig. S18 Time resolved fluorescence spectra (TRPL) of P1 in CH 3 CN (% and 8% of water) and A1 in THF (% and 6% of water) measured after 18 hours. S17
This journal is The Royal Society of Chemistry 212 Table S1. Time-resolved fluorescence decay constants of P1 and A1, sensor complexes and their aggregation induced emissions concentrations. Compound τ 1 (ns) τ 2 (ns) A 1 (%) A 2 (%) τ Avg (ns) P1.2321 1.8891 35.58 64.42 1.3 P1+Cu 2+ 1.8491 6.96 96.16 3.84 2.5 P1 (8%) 3.2516 6.296 71.31 28.69 4.13 A1 3.444 11.7947 14.31 85.69 1.6 A1+Fe 3+ 5.945 14.7 23.51 76.49 12.46 A1 (6%) 1.9563 24.17 8.4 91.6 22.3 Notes and References 1 R. A. Robinson, and R. H. Stokes, Electrolyte solutions" 2nd ed., rev., 1968, London, Butterworths. 2 K. Krzysztof, I. and Kuzniarska-Biernacka, Struct. Chem., 21, 21, 357. 3 C. G. Freiherr von Richthofen, A. Stammler, H. Bogge, and T. Glaser, J. Org. Chem., 212, 77, 1435. 4 Q. Mei, L. Wang, B. Tian, F. Yan, B. Zhang, W. Huang, and B. Tong, New J. Chem., 212, 36, 1879. 5 Y. Kubo, M. Kato, Y. Misawa, and S. Tokita, Tetrahedron Lett., 24, 45, 3769. S18