Supplementary Information Tuning the Luminescence of Metal-Organic Frameworks for Detection of Energetic Heterocyclic Compounds Yuexin Guo, Xiao Feng,*, Tianyu Han, Shan Wang, Zhengguo Lin, Yuping Dong, and Bo Wang*, Contents Section A. Materials and methods Section B. Synthetic procedures Section C. Single crystal structure determinations Section D. Supplementary spectra (Figure S1-S11) Section E. Supporting references S1
Section A. Materials and methods All chemicals and reagents were purchased from Alfa Aesar and Beijing Chemical Reagent Company without further purification. Solvents were purified according to standard procedures. 1 H NMR spectra were recorded on a Bruker ARX-400 spectrometer. MALDI-TOF-MS spectra were measured by a Bruker BIFLEX III spectrometer. UV-vis absorption spectra were recorded on a TU-1901 spectrophotometer. Fluorescence spectra were carried out on an F-4500 spectrophotometer. Single crystal X-ray diffractions were measured on a Bruker Smart Apex diffractometer equipped with a Mo-Kα sealed-tube X-ray source (λ = 0.71073 Å, graphite monochromated). IR spectra were performed on an IRPrestige-21 spectrometer using KBr pellets in the frequency range of 4000-500 cm -1. Elemental analyses were measured by VARIO EL-III Elemental Analyzer. The fluorescence spectra measurement conditions for the detection of NTO solution at different concentrations in THF/Hexane mixtures: v(thf):v(hexane) = 1:9, [TABD-MOF-3] = 0.03 mg/ml. The fluorescence spectra measurement conditions for the detection of different analytes in solution: TABD-MOF-3: v(thf):v(hexane) = 1:9, [TABD-MOF-3] = 0.03 mg/ml, [analyte] = 10-3 mol/l, the concentration of AT, DAT, HAT and 5-ATZ is 10-5 mol/l due to their relatively low solubility in THF. The detection limit is calculated on the basis of the fluorescence titration. The fluorescence emission spectrum of TABD-MOF-3 was measured 6 times, and the standard deviation of blank measurement was achieved. To gain the slope, the ratio of maximum emission intensity was plotted as a concentration of NTO (0~5 10-8 ). The detection limit is calculated using the following equation: S2
Detection limit = 3 x σ/k Where σ is the standard deviation of blank measurement, and K is the slope between the ratio of emission intensity versus [NTO] near the detection limit. The detection limit is calculated to be 4 10-8 mol/l. Further, the detection experiments was repeated 5 times under the same condition (THF/Hexane = 1:9, [NTO]: 4 10-8 ~10-3 mol/l), where the results showed a linear relationship between I/I 0 and lg(c NTO ): I/I 0 = 5.31252 lg(c NTO ) + 44.04818 (r = 0.993). The relative standard deviation of a given set of readings varied in the range 4.3-9.6% for NTO, depending on the concentration. These results were further validated by UV-Vis spectroscopy (the concentration of NTO that have been validated is in the range from 10-4 ~10-5 mol/l). S3
Section B. Synthetic procedures The ligand TABD-COOH was synthesized according to our previous report. 1 Synthesis of MOFs: M(C 30 H 22 O 4 ) x (DMF) y (M = Mg, Ni, Co) The solution of metal nitrate (0.02 mmol/l) and TABD-COOH (0.01 mmol/l) in DMF were prepared. TABD-MOFs was synthesized by reacting the mixture solvents of 1 ml M(NO 3 ) 2 6H 2 O (0.02 mmo/l), 1 ml TABD-COOH, 0.5 ml H 2 O and 0.5 ml ethanol at 85 o C for 24 h. Diamond-shaped single crystals were obtained for all compounds. TABD-MOF-1. Mg 2 (C 30 H 22 O 4 ) 3 (DMF) 4, transparent crystals, yield: 54% (based on Mg). Anal. calcd for C 102 H 88 Mg 2 N 4 O 16 : C, 73.12; H, 5.26; N, 3.35; found: C, 72.57; H, 5.88; N, 3.55. IR (KBr pellet, v/cm -1 ): 3432 (m), 1661 (s), 1555 (w), 1438 (vw), 1402 (s), 1344 (w), 1104 (m), 871 (w), 794 (m), 767 (w), 715 (w), 696 (m), 490 (w). TABD-MOF-2. Ni(C 30 H 22 O 4 ) 1 (DMF) 2, green crystals, yield: 65% (based on Ni). Anal. calcd for C 36 H 34 N 2 NiO 6 : C, 66.59; H, 5.28; N, 4.31; found: C, 63.82; H, 4.30; N, 4.15. IR (KBr pellet, v/cm -1 ): 3402 (m), 1642 (s), 1582 (vw), 1521 (w), 1421 (m), 1378 (m), 1104 (s), 859 (m), 789 (w), 764 (w), 715 (w), 687 (m), 498 (w). TABD-MOF-3. Co(C 30 H 22 O 4 ) 1 (DMF) 2, pink crystals, yield: 78% (based on Co). Anal. calcd for C 36 H 34 N 2 CoO 6 : C, 66.56; H, 5.28, N, 4.31; found: C, 66.09; H, 5.34, N, 4.24. IR (KBr pellet, v/cm -1 ): 3423 (m), 1647 (s), 1525 (s), 1437 (vw), 1418 (s), 1382 (m), 1107 (m), 855 (s), 791 (m), 765 (m), 739 (m), 716 (m), 685 (s), 497 (m). S4
Section C. Single crystal structure determinations Crystals coated with Paratone oil on a Cryoloop pin were measured on Bruker Smart Apex diffractometer equipped with a Mo-Kα sealed-tube X-ray source (λ = 0.71073 Å, graphite monochromated) and a cooling device (110 K). The crystal structures were solved by Direct Methods and refined on F 2 by full-matrix least-squares using the Shelxtl-97 program systems. Details of crystal data, data collection, structure solution, and refinement are given in Table S1, S2 and S3. CCDC 1009150, 1009690 and 1009691 contain the crystallographic data for these structures. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. S5
Table S1. Crystal data and structure refinement for TABD-MOF-1. Identification code Empirical formula Formula weight Temperature Wavelength Crystal system Space group Unit cell dimensions TABD-MOF-1 C 102 H 88 Mg 2 N 4 O 16 1674.38 153(2) K 0.71073 Å Triclinic P-1 a = 9.0000(2) Å a =83.0 o. b = 15.000(3) Å b = 77.0 o. c = 17.000(3) Å g = 87.0 o. Volume Z Calculated density Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected / unique Completeness to theta = 25.02 Refinement method Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2sigma(I)] R indices (all data) Largest diff. peak and hole 2218.8(7) Å ^3 1 1.253 Mg/m 3 0.097 mm -1 880 0.21 x 0.14 x 0.1 mm 3 2.38 to 25.02 o. -10<=h<=10, -17<=k<=17, -20<=l<=20 18910 / 7779 [R(int) = 0.0270] 99.2 % Full-matrix least-squares on F 2 7779 / 0 / 563 1.031 R1 = 0.0409, wr2 = 0.1076 R1 = 0.0498, wr2 = 0.1140 0.502 and -0.193 e. Å -3 S6
Table S2. Crystal data and structure refinement for TABD-MOF-2. Identification code Empirical formula Formula weight Temperature Wavelength Crystal system Space group Unit cell dimensions TABD-MOF-2 C 36 H 34 N 2 NiO 6 649.34 153(2) K 0.71073 Å Triclinic P-1 a = 6.0000(1) Å a = 97.7 o. b = 7.0000(1) Å b = 96.8 o. c = 17.544(3) Å g = 96.0 o. Volume Z Calculated density Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected / unique Completeness to theta = 25.01 Refinement method Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2sigma(I)] R indices (all data) Largest diff. peak and hole 719.6(2) Å ^3 1 1.498 Mg/m 3 0.728 mm -1 340 0.27 x 0.11 x 0.05 mm 3 2.36 to 25.01 o. -7<=h<=7, -8<=k<=8, -20<=l<=20 7013/ 2538 [R(int) = 0.0195] 99.6 % Full-matrix least-squares on F 2 2538 / 0 / 207 1.080 R1 = 0.0294, wr2 = 0.0745 R1 = 0.0320, wr2 = 0.0758 0.331 and -0.338 e. Å -3 S7
Table S3. Crystal data and structure refinement for TABD-MOF-3. Identification code Empirical formula Formula weight Temperature Wavelength Crystal system Space group Unit cell dimensions TABD-MOF-3 C 36 H 34 N 2 CoO 6 649.58 153(2) K 0.71073 Å Triclinic P-1 a = 6.0000(1) Å a = 96.7 o. b = 7.0000(1) Å b = 96.9 o. c = 17.422(3) Å g = 96.0 o. Volume Z Calculated density Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected / unique Completeness to theta = 25.02 Refinement method Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2sigma(I)] R indices (all data) Largest diff. peak and hole 716.6(2) Å ^3 1 1.506 Mg/m 3 0.653 mm -1 339 0.31 x 0.16 x 0.05 mm 3 2.38 to 25.02 o. -7<=h<=7, -8<=k<=8, -20<=l<=20 6990 / 2531 [R(int) = 0.0180] 99.8 % Full-matrix least-squares on F 2 2531 / 0 / 207 1.087 R1 = 0.0291, wr2 = 0.0773 R1 = 0.0309, wr2 = 0.0785 0.325 and -0.285 e. Å -3 S8
Section D. Supplementary spectra (Figure S1-S11) Figure S1. PXRD patterns of a) TABD-MOF-1, b) TABD-MOF-2, and c) TABD-MOF-3. S9
Figure S2. Normalized fluorescence emission spectra of TABD-MOF-1, TABD-MOF-2, and TABD-MOF-3. Excitation wavelength: 360 nm. S10
Figure S3. (a) Impact sensitivity and detonation velocity of NTO, TNT, RDX, and HMX. (b) Illustration of the turn-on detection of NTO by MOF-deposited paper strips (amount of MOF < 0.1 mg) via fluorescence approach. S11
Figure S4. Fluorescence spectra of the TABD-MOFs-deposited paper strips upon addition of explosives. The inserts are photographs of the TABD-MOFs-deposited paper strips before and after detection of NTO under UV illumination. Excitation wavelength: 360 nm. S12
Figure S5. Photograghs of TABD-MOF-3-deposited strip paper upon addition of NTO under UV light taken at different times. S13
Figure S6. Fluorescence spectra of the TABD-MOF-3-deposited paper strips upon addition of 10 µl THF solution of NTO at different concentrations under UV-light (365 nm). S14
Figure S7. (a) The mixtures in the left bottles in each photograph are THF solutions of TABD-MOFs, the mixtures in the middle bottles are THF solutions of TABD-MOFs with addition of NTO THF solution, and the mixtures in the right bottles are THF and hexane mixture solutions (v(thf):v(hexane) = 1:9) of TABD-MOFs with addition of NTO THF solution. (b) Plot of I/I 0 versus lg(c NTO ) for TABD-MOF-3 upon addition of different amount of NTO. I/I 0 = 5.31252 lg(c NTO ) + 44.04818 (r = 0.993). S15
Figure S8. (a) Matrix-assisted laser desorption ionization time-of-flight mass spectrum of TABD-MOF-1+NTO. (b) High-resolution mass spectrum of TABD-MOF-3+NTO. The peaks centred at m/z = 129.01, 188.95, 259.02, and 445.14 can be attributed to [NTO] -, [NTO+Co], [3NTO+2Co+H 2 O] 2- and [TABD-COOH], respectively. (c) 1 H NMR spectra of TABD-MOF-1+NTO, TABD-COOH, and NTO. (TABD-MOF-1+NTO and NTO were measured in d 8 -THF, and TABD-COOH was measured in d 6 -DMSO. 1 H NMR spectra of TABD-MOF-3 and TABD-MOF-2 could not be obtained due to paramagnetic properties of Co 2+ and Ni 2+ ion.) S16
Figure S9. (a) Fluorescence spectra of TABD-COOH and TABD-MOFs with addition of NTO solution in the mixture solvents (v(thf):v(hexane) = 1:9). Excitation wavelength: 360 nm. (b) UV spectra of TABD-COOH and TABD-MOFs with addition of NTO solution in the mixture solvents (v(thf):v(hexane) = 1:9). (c-d) Fluorescence spectra of TABD-COOH and TABD-COOK with addition of NTO solution in the mixture solvents (v(thf):v(hexane) = 1:9). Excitation wavelength: 360 nm. S17
Figure S10. Photographs of TABD-MOF-3-deposited, TABD-COOH-deposited, and TABD-COOK-deposited strip papers upon addition of different anayltes under UV illumination. The concentrations of the analytes in solid state is 10-3 mol L -1 in THF, and the analytes in liquid state are directly used for the detection without dilution. S18
Figure S11. Fluorescence enhanced efficiencies ((I-I 0 )/I 0 ) obtained from different analytes by TABD-MOF-3. S19
Section E. Supporting references 1. T. Han, Y. Zhang, X. Feng, Z. Lin, B. Tong, J. Shi, J. Zhi, Y. Dong, Chem. Commun., 2013, 49, 7049-7051. S20