Supporting Information Unprecedented solvent-dependent sensitivities in highly efficient detection of metal ions and nitroaromatic compounds by a fluorescent Ba MOF Rongming Wang, Xiaobin Liu, Ao Huang, Wen Wang, Zhenyu Xiao, Liangliang Zhang, Fangna Dai, Daofeng Sun* State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), College of Science, China University of Petroleum (East China), Qingdao Shandong 266580, China. *To whom correspondence should be addressed. E-mail: dfsun@upc.edu.cn - S1 -
(1)Experimental Procedures Unless otherwise noted, all reagents were obtained from commercial suppliers and used without further purification. 1 H NMR spectra was measured on a Bruker AVANCE-300 NMR Spectrometer. X-ray powder diffractions were measured on a Panalytical X-Pert pro diffractometer with Cu-Kα radiation. Elemental analyses (C, H, N) were obtained on a PerkinElmer 240 elemental analyzer. The thermogravimetric analysis (TGA) was carried out between room temperature and 600 C in a static N 2 with a heating rate of 10 C/min. Photoluminescence spectra were measured on F-2700 fluorescence spectrophotometer. The fluorescent detections of metal ions or aromatic compounds were performed by the incremental addition of analytes (0 to 70 µl) to 3 ml of emusions of UPC-17. The emusion was obtained by adding 2 mg of UPC-17 into 3 ml of solvent, and ultrasonically dispersing 20 minutes. The 10 mmol dm -3 of analyte was prepared by using the same solvent with the detecting emulsion. - S2 -
(2) Synthesis of ligand and UPC-17 Synthesis of H 2 ADDA. A 250 ml three-necked flask with magneton was charged with a mixture of 9,10-dibromoanthracene (3.36 g, 10 mmol), Pd(OAc) 2 (90 mg, 0.402 mmol) and tris(o-tolyl)phosphine (580 mg, 1.908 mmol). The flask was degassed and filled with nitrogen, which was repeated for three times. Waterless Et 3 N (80 ml) were added by a syring under nitrogen. After this, methyl acrylate (2.5 ml, 27.616 mmol) was added to the solution. The reaction mixture was heated to 100 in an oil bath for 2 days under N 2 atmosphere. After the mixture was cooled to room temperature and concentrated with a rotary evaporator, it was extracted with CH 2 Cl 2 and washed three times with H 2 O. The organic layer was then dried with MgSO 4, and the solvent was removed with rotary evaporator. The resulting crude product was purified by column chromatography (CHCl 3 as the eluent). The product was obtained after removal of the solvents (2.4 g, 69.4% yield). 1 H NMR (400 MHz, CDCl 3 ): δ 8.61 (d, 2H); 8.25 (q, 4H); 7.54 (q, 4H); 6.43 (d, 2H); 3.93 (s, 6H). - S3 -
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To a suspension of (2E,2'E)-dimethyl 3,3'-(anthracene-9,10-diyl)diacrylate (2.4 g, 6.9 mmol) in 30 ml THF was added 30 ml MeOH and 40 ml 3M aqueous KOH solution. The mixture was heated at 60 overnight. After this, the mixture was cooled to room temperature, it was poured into an ice/hcl mixture, then followed by filtration, and washed several times with H 2 O. The product (2.08 g, 65.4%) was obtained after the organic layer was collected and the solvent was removed via rotary evaporator. 1 H NMR (400 MHz, DMSO-d 6 ): δ 12.85 (s, 2H); 8.50 (d, 2H); 8.23 (q, 4H); 7.64 (q, 4H); 6.34 (d, 2H). - S5 -
Synthesis of UPC-17. A mixture of Ba(NO 3 ) 2 (26 mg, 0.12 mmol), H 2 ADDA (3 mg, 0.01 mmol), 2 ml of DMF-EtOH-H 2 O (v/v/v = 5:2:1) was sealed in a pressure-resistant glass tube, heated to 90 C during 8 hours, kept at 90 C for 48 hours, and then slowly cooled to 30 C during 10 hours. Pale yellow crystals were collected, washed with EtOH and dried in air (yield: 70%). Elemental analysis calcd (%) for UPC-17 (Ba 5 (ADDA) 5 (EtOH) 2 (H 2 O) 3 5DMF/ Ba 5 C 119 H 113 O 30 N 5 ): C 51.42%, H 4.10%, N 2.52%; found: C 51.08, H 3.99, N 2.54 %. - S6 -
(3) Crystal structure determination of UPC-17 Crystal structure determination of UPC-17: Single-crystal X-ray diffraction was performed using an Aglient technologies SuperNova Atlas Dual System, with a (Mo Kα λ = 0.71073 Å) microfocus source and focusing multilayer mirror optics. Structure was solved by direct methods using SHELXTL and refined by full-matrix least-squares on F 2 using SHELX-97. Non-hydrogen atoms were refined with anisotropic displacement parameters during the final cycles. Hydrogen atoms were placed in calculated positions with isotropic displacement parameters set to 1.2 U eq of the attached atom. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited in the Cambridge Crystallographic Data Center with CCDC Number: 1404807. - S7 -
Table S1. Crystal Data Collection and Structure Refinement for UPC-17. UPC-17 formula C 119 H 113 N 5 O 30 Ba 5 Mr 2779.82 size [mm 3 ] 0.13 0.10 0.08 crystal system Triclinic space group P-1 a [Å] 10.8177(3) b [Å] 19.8483(6) c [Å] 25.8687(5) α [ o ] 101.117(2) β [ o ] 101.1081(18) γ [ o ] 94.827(2) V [Å 3 ] 5305.4(2) Z 4 F(000) 672 ρcalcd [g cm -3 ] 1.473 [mm -1 ] 7.45 range [ o ] 3.49 to 25.00 Reflec. collected 2231 Indep. reflec. 1722 (Rint = 0.0435) parameters 203 R1 [I > 2σ(I)] 0.0604 wr2 [I > 2σ(I)] 0.1729 goodness of fit 1.085 - S8 -
(4) Additional figures for UPC-17 Figure S1. The coordination environments of the five crystallographically independent barium ions in UPC-17. Figure S2. The coordination modes of the five crystallographically independent organic ligands with trans conformation (a, b, c) and cis conformation (d, e) in UPC-17. - S9 -
Figure S3. The 3D packing of UPC-17 along a axis showing the trans conformation (grey color) and cis conformation (red color) of the ligands. - S10 -
(5) TGA of UPC-17 Figure S4. TGA curve of UPC-17. (6) IR spectrum of UPC-17 4000 3500 3000 2500 2000 1500 1000 500 0 Figure S5. The IR spectrum of UPC-17. Wavelength / nm - S11 -
(7) pxrd of UPC-17 Figure S6. The pxrd of UPC-17. - S12 -
(7) Photoluminescence spectrum of UPC-17 Figure S7. The solid state photoluminescence of UPC-17 at room temperature and 77K upon 330 nm excitation. Intensity 4500 4000 3500 3000 2500 2000 1500 1000 500 0 DMSO EtOH CH3CN Isopropanol THF Acetone MeOH CH2Cl2 DMF Dioxane Cyclohexane Toluene Nitrobenzene 400 450 500 550 600 650 700 Wavelength / nm Figure S8. The emission spectra of emulsion of UPC-17 dispersed in different solvents. - S13 -
Figure S9. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Ca 2+ ion (10 mmol/l). Figure S10. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Cd 2+ ion (10 mmol/l). - S14 -
Figure S11. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Al 3+ ion (10 mmol/l). Figure S12. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Mg 2+ ion (10 mmol/l). - S15 -
Figure S13. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Pb 2+ ion (10 mmol/l). Figure S14. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Zn 2+ ion (10 mmol/l). - S16 -
Figure S15. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Ag + ion (10 mmol/l). Figure S16. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Cu 2+ ion (10 mmol/l). - S17 -
Figure S17. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Fe 3+ ion (10 mmol/l). Figure S18. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Co 2+ ion (10 mmol/l). - S18 -
Figure S19. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of Mn 2+ ion (10 mmol/l). Figure S20. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Ca 2+ ion (10 mmol/l). - S19 -
Figure S21. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Cd 2+ ion (10 mmol/l). Figure S22. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Al 3+ ion (10 mmol/l). - S20 -
Figure S23. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Mg 2+ ion (10 mmol/l). Figure S24. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Pb 2+ ion (10 mmol/l). - S21 -
Intensity 6000 5000 4000 3000 2000 0 ul 1 ul 3 ul 5 ul 10 ul 20 ul 30 ul 50 ul 70 ul 1000 0 400 450 500 550 600 650 700 Wavelength / nm Figure S25. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Zn 2+ ion (10 mmol/l). 6000 Intensity 5000 4000 3000 2000 1000 0 ul 1 ul 3 ul 5 ul 10 ul 20 ul 30 ul 50 ul 70 ul 0 400 450 500 550 600 650 700 Wavelength / nm Figure S26. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Ag + ion (10 mmol/l). - S22 -
Figure S27. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Cu 2+ ion (10 mmol/l). Figure S28. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Fe 3+ ion (10 mmol/l). - S23 -
Figure S29. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Co 2+ ion (10 mmol/l). Figure S30. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of Mn 2+ ion (10 mmol/l). - S24 -
Figure S31. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Ca 2+ ion (10 mmol/l). Figure S32. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Cd 2+ ion (10 mmol/l). - S25 -
Figure S33. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Al 3+ ion (10 mmol/l). Figure S34. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Mg 2+ ion (10 mmol/l). - S26 -
Figure S35. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Pb 2+ ion (10 mmol/l). Figure S36. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Zn 2+ ion (10 mmol/l). - S27 -
Figure S37. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Ag + ion (10 mmol/l). Figure S38. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Cu 2+ ion (10 mmol/l). - S28 -
Figure S39. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Fe 3+ ion (10 mmol/l). Figure S40. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Co 2+ ion (10 mmol/l). - S29 -
Figure S41. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of Mn 2+ ion (10 mmol/l). Figure S42. Photoluminescence intensity upon the addition of mixed metal ions into the MeOH-emulsion of UPC-17. - S30 -
Figure S43. Photoluminescence intensity upon the addition of mixed metal ions into the THF-emulsion of UPC-17. Figure S44. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of nitrobenzene (NB) (10 mmol/l). - S31 -
Figure S45. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of 1,4-dinitrobenzene (10 mmol/l). Figure S46. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of chlorobenzene (10 mmol/l). - S32 -
Figure S47. The emission spectra of an emulsion of UPC-17 dispersed in MeOH upon gradual addition of 4-nitrophenol (4-NP) (10 mmol/l). Figure S48. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of nitrobenzene (NB) (10 mmol/l). - S33 -
Figure S49. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of 1,4-dinitrobenzene (10 mmol/l). Figure S50. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of chlorobenzene (10 mmol/l). - S34 -
Figure S51. The emission spectra of an emulsion of UPC-17 dispersed in acetone upon gradual addition of 4-nitrophenol (4-NP) (10 mmol/l). Figure S52. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of nitrobenzene (NB) (10 mmol/l). - S35 -
Figure S53. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of 1,4-dinitrobenzene (10 mmol/l). Figure S54. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of chlorobenzene (10 mmol/l). - S36 -
Figure S55. The emission spectra of an emulsion of UPC-17 dispersed in THF upon gradual addition of 4-nitrophenol (4-NP) (10 mmol/l). Figure S56. The emission spectra of an emulsion of H 2 ADDA dispersed in MeOH upon gradual addition of Fe 3+ ion (10 mmol/l). - S37 -
Figure S57. The emission spectra of an emulsion of H 2 ADDA dispersed in MeOH upon gradual addition of Al 3+ ion (10 mmol/l). Figure S58. The emission spectra of an emulsion of H 2 ADDA dispersed in MeOH upon gradual addition of 4-nitrophenol (4-NP) (10 mmol/l). - S38 -
Figure S59. The emission spectra of an emulsion of H 2 ADDA dispersed in THF upon gradual addition of Fe 3+ ion (10 mmol/l). Figure S60. The emission spectra of an emulsion of H 2 ADDA dispersed in THF upon gradual addition of Al 3+ ion (10 mmol/l). - S39 -
Figure S61. The emission spectra of an emulsion of H 2 ADDA dispersed in THF upon gradual addition of 4-nitrophenol (4-NP) (10 mmol/l). Figure S62. UV-vis spectra UPC-17 dispersed in, a) THF, and b) MeOH treated with corresponding Fe 3+ ion concentration. - S40 -
(9) Stern-Volmer plots of UPC-17 Figure S63. The Stern Volmer plots for UPC-17 with Fe(NO 3 ) 3 in MeOH solutions. Figure S64. The Stern Volmer plots for UPC-17 with Al(NO 3 ) 3 in MeOH solutions. - S41 -
Figure S65. The Stern Volmer plots for UPC-17 with Fe(NO 3 ) 3 in THF solutions. Figure S66. The Stern Volmer plots for UPC-17 with Al(NO 3 ) 3 in THF solutions. - S42 -
Figure S67. The Stern Volmer plots for UPC-17 with 4-nitrophenol (4-NP) in MeOH solutions. Figure S68. The Stern Volmer plots for UPC-17 with 4-nitrophenol (4-NP) in Acetone solutions. - S43 -
Figure S69. The Stern Volmer plots for UPC-17 with 4-nitrophenol (4-NP) in THF solutions. Figure S70. Detection limit (D) of Fe(NO 3 ) 3 in MeOH solutions for UPC-17. - S44 -
Figure S71. Detection limit (D) of Al(NO 3 ) 3 in MeOH solutions for UPC-17. Figure S72. Detection limit (D) of 4-nitrophenol (4-NP) in MeOH solutions for UPC-17. - S45 -
Figure S73. Detection limit (D) of Fe(NO 3 ) 3 in Acetone solutions for UPC-17. Figure S74. Detection limit (D) of Al(NO 3 ) 3 in Acetone solutions for UPC-17. - S46 -
Figure S75. Detection limit (D) of 4-nitrophenol (4-NP) in Acetone solutions for UPC-17. Figure S76. Detection limit (D) of Fe(NO 3 ) 3 in THF solutions for UPC-17. - S47 -
Figure S77. Detection limit (D) of Al(NO 3 ) 3 in THF solutions for UPC-17. Figure S78. Detection limit (D) of 4-nitrophenol (4-NP) in THF solutions for UPC-17. - S48 -