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1 Supporting Information Exploring the detection of metal ions by tailoring the coordination mode of V-shaped thienylpyridyl ligand in three MOFs Li-Juan Han,, Wei Yan, Shu-Guang Chen, Zhen-Zhen Shi, and He-Gen Zheng*, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing , P. R. China. Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry and Chemical Engineering, Jining University, Qufu, , P. R. China. S-1

2 Content Materials and instrumentation...4 Scheme S1. BPTP and OBA Ligand Synthesis of 3,5-bis(5-(pyridin-4-yl)thiophen-2-yl)pyridine (BPTP). 4 Synthesis of compound Synthesis of compound Synthesis of compound Figure S1. 1 H NMR spectrum of BPTP 6 Figure S2. FT-IR spectroscopy of BPTP.. 6 Figure S3. Solid-state UV-vis absorbance spectra of BPTP and Figure S4. TGA plot of Figure S5. Solid-state PL spectra of BPTP, and complex Figure S6. Liquid-state PL spectra of BPTP, and complex Figure S7. PL spectra of BPTP DMF suspension.. 9 Figure S8. PL spectra of 1 before and after adding different metal ions..10 Figure S9. PL spectra of 2 before and after adding different metal ions Figure S10. PL spectra of 3 before and after adding different metal ions 13 Figure S11. The fitting curve of the emission intensity of 1 vs. Fe 3+ concentration. 15 Figure S12. The fitting curve of the emission intensity of 2 vs. Fe 3+ concentration. 15 Figure S13. The fitting curve of the emission intensity of 3 vs. Fe 3+ concentration. 16 Figure S14. Photographs showing color changes of 1 after adding Fe 3+ ions 16 Figure S15. Photographs showing color changes of 2 after adding Fe 3+ ions 17 Figure S16. Photographs showing color changes of 3 after adding Fe 3+ ions 17 Figure S17. PXRD of 1 before and after immersed in Fe 3+ / Cu 2+ ions 80 hours...18 Figure S18. PXRD of 2 before and after immersed in Fe 3+ / K + ions 80 hours..18 Figure S19. PXRD of 3 before and after immersed in Fe 3+ / Al 3+ ions 80 hours 19 Figure S20. FT-IR spectrum of Figure S21. FT-IR spectrum of 1 after immerged in Fe 3+ ( M) 80 hours...20 Figure S22. FT-IR spectrum of 1 after immerged in Cu 2+ ( M) 80 hours S-2

3 Figure S23. FT-IR spectrum of Figure S24. FT-IR spectrum of 2 after immerged in Fe 3+ ( M) 80 hours. 21 Figure S25. FT-IR spectrum of 2 after immerged in K + ( M) 80 hours. 22 Figure S26. FT-IR spectra of 2 before and after immersed in different ions Figure S27. FT-IR spectrum of Figure S28. FT-IR spectrum of 3 after immerged in Fe 3+ ( M) 80 hours. 23 Figure S29. FT-IR spectrum of 3 after immerged in Al 3+ ( M) 80 hours. 24 Figure S30. FT-IR spectra of 3 before and after immersed in Fe 3+ /Al Figure S31. Survey XPS spectrum of Figure S32. Survey XPS spectrum of 1 after immersed in Cu h..25 Figure S33. Survey XPS spectrum of 1 after immersed in Fe h Figure S34. N 1S XPS spectrum of 2 before and after immersed in Fe 3+ /K Figure S35. Survey XPS spectrum of Figure S36. Survey XPS spectrum of 2 after immersed in Fe h. 27 Figure S37. Survey XPS spectrum of 2 after immersed in K + 80 h 28 Figure S38. N 1S XPS spectrum of 3 before and after immersed in Fe 3+ /Al Figure S39. Survey XPS spectrum of Figure S40. Survey XPS spectrum of 3 after immersed in Al h. 29 Figure S41. Survey XPS spectrum of 3 after immersed in Fe h. 29 Figure S42. PL spectra of 1 before and after adding different anions 30 Figure S43. PL spectra of 2 before and after adding different anions 31 Figure S44. PL spectra of 3 before and after adding different anions 32 Table S1. Performance comparison between MOFs fluorescent sensors for Fe Table S2 Crystal data and structure refinement for 1 and 2 33 Table S3 Crystal data and structure refinement for 3.34 Table S4 Selected bond lengths (Å) and angles ( ) for 1 and 2 and S-3

4 Materials and instrumentation All Reagents and solvents except BPTP ligand were of commercially available and used as received without further purification. NMR spectra were recorded on a Bruker NMR 500 DRX spectrometer. The IR absorption spectra of these complexes were recorded in the range of cm -1 by means of a Nicolet (Impact 410) spectrometer with KCl pellets. Element analyses (C, H, N) were carried out on a Perkin-Elmer model 240C analyzer. PXRD measurements were performed on a Bruker D8 Advance X-ray diffractometer using Cu-Kα radiation ( nm), in which the X-ray tube was operated at 40 kv and 30 ma. Thermogravimetric analysis was performed on a Perkin Elmer thermogravimetric analyzer from room temperature to 800 C with a heating rate of 10 K min -1 under N2 atmosphere. Solid-state UV-vis diffuse reflectance spectra were obtained at room temperature using Shimadzu UV-3600 double monochromator spectrophotometer, and BaSO4 was used as a 100% reflectance standard for all materials. Photoluminescence spectra for the solid samples were recorded with a PerkinElmer FS-LS55 fluorescence spectrophotometer at room temperature. Scheme S1. BPTP and OBA Ligand. Synthesis of 3,5-bis(5-(pyridin-4-yl)thiophen-2-yl)pyridine (BPTP): 3,5-bis(5- bromothiophen-2-yl)pyridine (3g, 7.48 mmol), 4-pyridineboronic acid (2.76g, mmol), Pd(PPh 3 ) 4 (0.86 g, 0.75 mmol), 1,4-dioxane (70 ml) and 0.5 M K 2 CO 3 (aq) (25 ml) were mixed and refluxed for 48 hours under N 2. After cooling to room temperature, solvent was removed by distillation under a vacuum. The residue was washed by distilled water (3 80 ml), and purified by column chromatography (silica gel, methylene dichloride / Petroleum ether as the eluent) to afford yellow crystalline powder (yield: 72%, 2.40 g, based on 3,5-bis(5-bromothiophen-2-yl)pyridine). S-4

5 Synthesis of compound 1: A solution of DMF (5 ml) containing BPTP (0.024g, 0.06 mmol), 4,4'-oxydibenzoic acid (0.031g, 0.12 mmol), and Zn(OOCCH 3 ) 2 2H 2 O (0.026 g, 0.12 mmol) was placed in a Teflon vessel under autogenous pressure and heated at 95 C for 72 hours and then cooled to room temperature over 24 h. Yellow block-shaped crystals of 1 were obtained, washed with DMF and dried in air and collected in 58% yield based on the BPTP ligand. Elemental analysis calculated for C 51 H 31 N 3 O 10 S 2 Zn 2 : C, 58.86; H, 3.00; N, 4.04%. Found: C, 58.82; H, 2.95; N, 4.09%. Synthesis of compound 2: A mixture of Ni(NO 3 ) 2 6H 2 O (0.008g, 0.03 mmol), BPTP (0.012g, 0.03 mmol) and 4,4'-oxydibenzoic acid (0.008g, 0.03 mmol) in DMF (2.5 ml) and H 2 O (2.5 ml) were sealed in a Teflon-lined stainless steel autoclave. The autoclave was heated at 95 C for 3 days under autogenous pressure and then cooled to room temperature over 24 h. Green block-shaped crystals were obtained, washed with DMF and dried in air and collected in 42% yield based on the BPTP ligand. Elemental analysis calculated for C 74 H 52 N 6 NiO 12 S 4 : C, 63.30; H, 3.73; N, 5.98%. Found: C, 63.33; H, 3.71; N, 6.02%. Synthesis of compound 3: A mixture of Cd(NO 3 ) 2 4H 2 O (0.009g, 0.03 mmol), BPTP (0.012g, 0.03 mmol) and 4,4'-oxydibenzoic acid (0.016g, 0.06 mmol) in DMF (5 ml) and H 2 O (2.5 ml) were sealed in a Teflon-lined stainless steel autoclave. The autoclave was heated at 95 C for 3 days under autogenous pressure and then cooled to room temperature over 24 h. Yellow block-shaped crystals were obtained, washed with DMF and dried in air and collected in 46% yield based on the BPTP ligand. Elemental analysis calculated for C 51 H 31 Cd 2 N 3 O 11 S 2 : C, 53.23; H, 2.72; N, 3.65%. Found: C, 53.26; H, 2.70; N, 3.61%. S-5

6 Figure S1. 1 H NMR spectrum of BPTP. Figure S2. FT-IR spectroscopy of BPTP. S-6

7 Figure S3. Solid-state UV-vis absorbance spectra of BPTP and 1-3. Figure S4. TGA plot of 1-3. S-7

8 Figure S5. Solid-state photoluminescent spectra of BPTP, and complex 1-3 (monitored and excited at 474 nm and 370 nm for BPTP, monitored and excited at 431 nm and 396 nm for 1, monitored and excited at 487 nm and 408 nm for 2, monitored and excited at 489 nm and 391 nm for 3). S-8

9 Figure S6. Liquid-state photoluminescent spectra of BPTP, and complex 1-3 (monitored and excited at 420 nm and 281 nm for BPTP, monitored and excited at 404 nm and 346 nm for 1, monitored and excited at 407 nm and 291 nm for 2, monitored and excited at 404 nm and 345 nm for 3). Figure S7. PL spectra of BPTP DMF suspension (excited at 365 nm). S-9

10 S-10

11 Figure S8. PL spectra of 1 before and after adding different metal ions (excited at 370 nm). S-11

12 Figure S9. PL spectra of 2 before and after adding different metal ions (excited at 365 nm). S-12

13 S-13

14 Figure S10. PL spectra of 3 before and after adding different metal ions (excited at 310 nm). Detection limit was determined according to the following definitions: S is the slope of the calibration curve; Sb is the standard deviation for replicating detections of blank solutions. 1 S-14

15 Figure S11. The fitting curve of the emission intensity (excited at 370 nm) of 1 vs.fe 3+ concentration. Linear Equation: Y = X R 2 = S = M -1 S b = (n = 11) DL = 3Sb / S = M = 0.50 µm (for compound 1) Figure S12. The fitting curve of the emission intensity (excited at 365 nm) of 2 vs.fe 3+ concentration. Linear Equation: Y = X R 2 = S = M -1 S b = (n = 11) DL = 3Sb / S = M = 0.48 µm (for compound 2) S-15

16 Figure S13. The fitting curve of the emission intensity (excited at 310 nm) of 3 vs.fe 3+ concentration. Linear Equation: Y = X R 2 = S = M -1 S b = (n = 11) DL = 3Sb / S = M = 0.36 µm (for compound 3) Figure S14. Photographs showing color changes of 1 after adding Fe 3+ ions (a: under natural lighting; b: under 365 nm ultraviolet light). S-16

17 Figure S15. Photographs showing color changes of 2 after adding Fe 3+ ions (a: under natural lighting; b: under 365 nm ultraviolet light). Figure S16. Photographs showing color changes of 3 after adding Fe 3+ ions (a: under natural lighting; b: under 365 nm ultraviolet light). S-17

18 Figure S17. PXRD of 1 before and after immersed in Fe 3+ / Cu 2+ ions 80 hours. Figure S18. PXRD of 2 before and after immersed in Fe 3+ / K + ions 80 hours. S-18

19 Figure S19. PXRD of 3 before and after immersed in Fe 3+ / Al 3+ ions 80 hours. Figure S20. FT-IR spectrum of 1. S-19

20 Figure S21. FT-IR spectrum of 1 after immerged in Fe 3+ ( M) 80 hours. Figure S22. FT-IR spectrum of 1 after immerged in Cu 2+ ( M) 80 hours. S-20

21 Figure S23. FT-IR spectrum of 2. Figure S24. FT-IR spectrum of 2 after immerged in Fe 3+ ( M) 80 hours. S-21

22 Figure S25. FT-IR spectrum of 2 after immerged in K + ( M) 80 hours. Figure S26. FT-IR spectra of 2 before and after immersed in different ions. S-22

23 Figure S27. FT-IR spectrum of 3. Figure S28. FT-IR spectrum of 3 after immerged in Fe 3+ ( M) 80 hours. S-23

24 Figure S29. FT-IR spectrum of 3 after immerged in Al 3+ ( M) 80 hours. Figure S30. FT-IR spectra of 3 before and after immersed in Fe 3+ /Al 3+. S-24

25 Figure S31. Survey XPS spectrum of 1. Figure S32. Survey XPS spectrum of 1 after immersed in Cu h. S-25

26 Figure S33. Survey XPS spectrum of 1 after immersed in Fe h. Figure S34. N 1S XPS spectrum of 2 before and after immersed in Fe 3+ /K +. S-26

27 Figure S35. Survey XPS spectrum of 2. Figure S36. Survey XPS spectrum of 2 after immersed in Fe h. S-27

28 Figure S37. Survey XPS spectrum of 2 after immersed in K + 80 h. Figure S38. N 1S XPS spectrum of 3 before and after immersed in Fe 3+ /Al 3+. S-28

29 Figure S39. Survey XPS spectrum of 3. Figure S40. Survey XPS spectrum of 3 after immersed in Al h. Figure S41. Survey XPS spectrum of 3 after immersed in Fe h. S-29

30 Figure S42. PL spectra of 1 before and after adding different anions (excited at 370 nm). S-30

31 Figure S43. PL spectra of 2 before and after adding different anions (excited at 365 nm). S-31

32 Figure S44. PL spectra of 3 before and after adding different anions (excited at 310 nm). Table S1. Performance comparison between MOFs fluorescent sensors for Fe 3+. MOFs fluorescent sensors Detection Responsive time Reference limits (µm) Eu(acac) 3 Zn(C 15 H 12 NO 2 ) min 2 Tb(BTB)(DMF) 1.5DMF 2.5H 2 O 10 Seconds 3 MIL-53(Al) NUT-9-NS [Cd 2 (OBA) 2 (BPTP)(H 2 O)] Seconds Seconds Seconds 4 1 This work S-32

33 Table S2 Crystal data and structure refinement for 1 and 2. Empirical formula Formula weight Crystal color Crystal size (mm) Crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) Volume (Å 3 ) Z d calcd (g/cm 3 ) µ (mm -1 ) F (000) λ (Å) Temperature θ range (deg) h,k, l range Reflections collected / unique Completeness to θ Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2σ(I)] a R indices (all data) Largest diff. Peak and hole(e Å -3 ) 1 2 C 51 H 31 N 3 O 10 S 2 Zn Yellow 0.12 x 0.10 x 0.10 Monoclinic P2 1 /c (2) K 2.20 to <=h<=16-22<=h<=21-29<=h<= / [R(int) = ] 99.9 % (θ = 25.00) / 27 / R1 = wr2 = R1 = wr2 = and C 74 H 52 N 6 O 12 S 4 Ni Green 0.12 x 0.10 x 0.10 Triclinic P (18) (2) (3) (3) (3) (3) (5) (2) K 1.48 to <=h<=11-12<=h<=15-17<=h<= / 5682 [R(int) = ] 99.2 % (θ = 25.00) 5682 / 0 / R1 = wr2 = R1 = wr2 = and a R 1 = Σ Fo Fc /Σ Fo ; wr 2 = [Σw(Fo 2 Fc 2 ) 2 /ΣwFo 4 ] 1/2 S-33

34 Table S3 Crystal data and structure refinement for 3. Empirical formula Formula weight Crystal color Crystal size (mm) Crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) Volume (Å 3 ) Z d calcd (g/cm 3 ) µ (mm -1 ) F (000) λ (Å) Temperature θ range (deg) h,k, l range Reflections collected / unique Completeness to θ Data / restraints / parameters Goodness-of-fit on F 2 Final R indices [I>2σ(I)] b R indices (all data) Largest diff. Peak and hole(e Å -3 ) 3 C 51 H 31 N 3 O 11 S 2 Cd Yellow 0.10 x 0.10 x 0.08 Triclinic P (2) K 2.46 to <=h<=10-17<=k<=17-24<=l<= / 8578 [R(int) = % (θ = 27.47) 8757 / 0 / R1 = wr2 = R1 = wr2 = and b R 1 = Σ Fo Fc /Σ Fo ; wr 2 = [Σw(Fo 2 Fc 2 ) 2 /ΣwFo 4 ] 1/2 S-34

35 Table S4 Selected bond lengths (Å) and angles ( ) for 1, 2 and 3. 1 Zn(1)-N(1) 2.021(2) Zn(1)-O(10) 2.030(3) Zn(1)-O(9) 2.035(2) Zn(1)-O(7) 2.047(2) Zn(1)-O(6) 2.078(2) Zn(2)-O(3)# (3) Zn(2)-O(4)# (2) Zn(2)-N(2) 2.031(2) Zn(2)-O(5)# (2) Zn(2)-O(8)# (3) O(3)-Zn(2)# (3) O(4)-C(44) 1.260(4) O(4)-Zn(2)# (2) O(5)-Zn(2)# (2) O(8)-Zn(2)# (3) N(1)-Zn(1)-O(10) (11) N(1)-Zn(1)-O(9) (11) O(10)-Zn(1)-O(9) (9) N(1)-Zn(1)-O(7) (11) O(10)-Zn(1)-O(7) 90.84(11) O(9)-Zn(1)-O(7) 88.48(11) N(1)-Zn(1)-O(6) 96.52(10) O(10)-Zn(1)-O(6) 85.74(11) O(9)-Zn(1)-O(6) 87.95(11) Symmetry transformations used to generate equivalent atoms: #1 = x+1, y+1, z #2 = x-1, y-1, z S-35

36 2 Ni(1)-O(5)# (17) Ni(1)-O(5) (17) Ni(1)-O(6) (18) Ni(1)-O(6)# (18) Ni(1)-N(3) 2.111(2) Ni(1)-N(3)# (2) O(5)#1-Ni(1)-O(5) (1) O(5)#1-Ni(1)-O(6) 91.76(7) O(5)-Ni(1)-O(6) 88.24(7) O(5)#1-Ni(1)-O(6)# (7) O(5)-Ni(1)-O(6)# (7) O(6)-Ni(1)-O(6)# O(5)#1-Ni(1)-N(3) 91.66(7) O(5)-Ni(1)-N(3) 88.34(7) O(6)-Ni(1)-N(3) 91.68(8) O(6)#1-Ni(1)-N(3) 88.32(8) O(5)#1-Ni(1)-N(3)# (7) O(5)-Ni(1)-N(3)# (7) O(6)-Ni(1)-N(3)# (8) O(6)#1-Ni(1)-N(3)# (8) N(3)-Ni(1)-N(3)# (1) Symmetry transformations used to generate equivalent atoms: #1 = -x, -y+1, -z+1 S-36

37 3 Cd(1)-O(4) 2.226(5) Cd(1)-N(3) 2.257(5) Cd(1)-O(3) 2.269(6) Cd(1)-O(6) 2.338(5) Cd(1)-O(2) 2.392(6) Cd(1)-O(1) 2.482(5) Cd(2)-O(9)# (4) Cd(2)-O(10)# (4) Cd(2)-N(1)# (4) Cd(2)-N(2) 2.355(4) Cd(2)-O(7)# (4) Cd(2)-O(11)# (4) O(4)-Cd(1)-N(3) 112.2(2) O(4)-Cd(1)-O(3) 107.1(2) N(3)-Cd(1)-O(3) 138.0(2) O(4)-Cd(1)-O(6) 157.7(2) N(3)-Cd(1)-O(6) 88.69(18) O(3)-Cd(1)-O(6) 55.88(17) O(4)-Cd(1)-O(2) 82.5(2) N(3)-Cd(1)-O(2) 97.2(2) O(3)-Cd(1)-O(2) 102.3(2) O(4)-Cd(1)-O(1) 54.70(17) N(3)-Cd(1)-O(1) 88.64(17) O(3)-Cd(1)-O(1) (19) O(6)-Cd(1)-O(1) 137.4(2) O(2)-Cd(1)-O(1) 135.2(2) Symmetry transformations used to generate equivalent atoms: #1 = -x, -y, -z+2 #2 = x, y+1, z-1 #3 = x-1, y, z-1 #4 = x-1,y+1,z References 1. Xu, H.; Gao, J.; Qian, X.; Wang, J.; He, H.; Cui, Y.; Yang, Y.; Wang, Z.; Qian, G. Metal organic framework nanosheets for fast response and highly sensitive luminescent sensing of Fe 3+. J. Mater. Chem. A. 2016, 4, Qu, K.; Wang, J.; Ren, J.; Qu, X. Carbon Dots Prepared by Hydrothermal Treatment of Dopamine as an Effective Fluorescent Sensing Platform for the Label-Free Detection of Iron(III) Ions and Dopamine. Chem.-Eur. J. 2013, 19, Xu, H.; Hu, H.-C.; Cao, C.-S.; Zhao, B. Lanthanide Organic Framework as a Regenerable S-37

38 Luminescent Probe for Fe 3+. Inorg. Chem. 2015, 54, Yang, C.-X.; Ren, H.-B.; Yan, X.-P. Fluorescent Metal Organic Framework MIL-53(Al) for Highly Selective and Sensitive Detection of Fe 3+ in Aqueous Solution. Anal. Chem. 2013, 85, S-38

Supplementary Information

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,