Supplementary Information

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1 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

2 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 = Å, graphite monochromated). IR spectra were performed on an IRPrestige-21 spectrometer using KBr pellets in the frequency range of 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~ ). The detection limit is calculated using the following equation: S2

3 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 mol/l. Further, the detection experiments was repeated 5 times under the same condition (THF/Hexane = 1:9, [NTO]: ~10-3 mol/l), where the results showed a linear relationship between I/I 0 and lg(c NTO ): I/I 0 = lg(c NTO ) (r = 0.993). The relative standard deviation of a given set of readings varied in the range % 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

4 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, 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, 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, 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

5 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 = 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 , and contain the crystallographic data for these structures. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via S5

6 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 (2) K Å Triclinic P-1 a = (2) Å a =83.0 o. b = (3) Å b = 77.0 o. c = (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 = 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 (7) Å ^ Mg/m mm x 0.14 x 0.1 mm to o. -10<=h<=10, -17<=k<=17, -20<=l<= / 7779 [R(int) = ] 99.2 % Full-matrix least-squares on F / 0 / R1 = , wr2 = R1 = , wr2 = and e. Å -3 S6

7 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 (2) K Å Triclinic P-1 a = (1) Å a = 97.7 o. b = (1) Å b = 96.8 o. c = (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 = 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 ^ Mg/m mm x 0.11 x 0.05 mm to o. -7<=h<=7, -8<=k<=8, -20<=l<= / 2538 [R(int) = ] 99.6 % Full-matrix least-squares on F / 0 / R1 = , wr2 = R1 = , wr2 = and e. Å -3 S7

8 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 (2) K Å Triclinic P-1 a = (1) Å a = 96.7 o. b = (1) Å b = 96.9 o. c = (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 = 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 ^ Mg/m mm x 0.16 x 0.05 mm to o. -7<=h<=7, -8<=k<=8, -20<=l<= / 2531 [R(int) = ] 99.8 % Full-matrix least-squares on F / 0 / R1 = , wr2 = R1 = , wr2 = and e. Å -3 S8

9 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

10 Figure S2. Normalized fluorescence emission spectra of TABD-MOF-1, TABD-MOF-2, and TABD-MOF-3. Excitation wavelength: 360 nm. S10

11 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

12 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

13 Figure S5. Photograghs of TABD-MOF-3-deposited strip paper upon addition of NTO under UV light taken at different times. S13

14 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

15 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 = lg(c NTO ) (r = 0.993). S15

16 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 = , , , and 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

17 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

18 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

19 Figure S11. Fluorescence enhanced efficiencies ((I-I 0 )/I 0 ) obtained from different analytes by TABD-MOF-3. S19

20 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, S20