Fig. S2 XRPD patterns of 1 3.

Transcription

1 Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2018 Fig. S1 1 H NMR spectrum of NI bpy 34 in DMSO dd 6. Supporting Information for Luminescent Zn(II) coordination polymers as efficiently fluorescent sensors for highly sensitive detection of explosive nitroaromatics Meng Jung Tsai, Chih Yu Li, and Jing Yun Wu* Department of Applied Chemistry, National Chi Nan University, Nantou 545, Taiwan. E mail: jyunwu@ncnu.edu.tw

2 1 2 3 Fig. S2 XRPD patterns of

3 Fig. S3 Coordination environment around the Zn(II) center in 1. Fig. S4 Coordination environment around the Zn(II) center in 2. 2

4 Fig. S5 Crystal structure of 2: (top) view of the 3D H bonded network slight off the crystallographic a axis; (bottom) highlight of the layer to layl yer H bonding interactions (black dash lines). 3

5 Fig. S6 Coordination environment around the Zn(II) center in 3. Table S1. Important hydrogen bond data forr 1 3 a D H A d(d H) [Å] d(h A) [Å] 1 O6 H101 O8# O5 H5A O8#1 O9 H101 O2# O8 H101 O11#1 O8 H101 O15#1 O9 H102 O3#2 O9 H103 O6# d(d A) [Å] 2.660(2) 2.587(15) 2.984(12) 2.483(16) 3.36(2) 2.754(6) 2.682(6) (D H A) [ ] a Symmetry codes: For 1: #1, x, 1 y, 1 z; For 2: #1, 1 x, 1 y, 1 z; #2, 1 x, y, 1/2 z; For 3: #1, 1+x, y, 1+ +z; #2, x, 1 y, z. 4

6 Fig. S7 TG diagrams of

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8 Fig. S8 (Left) Fluorescence responses of 1 in toluene suspensionn (3.0 mg/3 3 ml) toward different concentrations of different nitro analyte.. (Right) Stern Volme plot for nitro analyte in the presence of toluene suspension of 1 in the range from 0 to 1.00 mm. m Inset shows the linear region for Stern Volmer analysis of 1 ass a function of concentration of nitro analyte. 7

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10 Fig. S9 (Left) Fluorescence responses of 2 in toluene suspensionn (3.0 mg/3 3 ml) toward different concentrations of different nitro analyte.. (Right) Stern Volme plot for nitro analyte in the presence of toluene suspension of 2 in the range from 0 to 1.00 mm. m Inset shows the linear region for Stern Volmer analysis of 2 ass a function of concentration of nitro analyte. 9

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12 Fig. S10 (Left) Fluorescence responses of 3 in toluene suspensionn (3.0 mg/33 ml) toward different concentrations of different nitro analyte.. (Right) Stern Volme plot for nitro analyte in the presence of toluene suspension of 3 in the range from 0 to 1.00 mm. m Inset shows the linear region for Stern Volmer analysis of 3 ass a function of concentration of nitro analyte. 11

13 (a) (b) (c) Fig. S11 (a c) Fluorescence quenching percentage of various nitro analytes att different concentrations ( mm) for the t toluenee suspensions of CPs

14 Fig. S12 Normalized UV Vis spectra of toluene solutions of nitro analytes and normalized fluorescence emission spectra off toluene suspensions of CPs

15 NI bpy 34 NB 1,,4 DNB 4 NT 2,,4 DNT 2 NP 3 NP 4 NP NM DMNB HOMO (ev) LUMO (ev) Energy E gap (ev) Fig. S13 HOMO and LUMO energies for NI bpy 34 and nitro analytes. 14

16 Measurements of limit of detection (LOD). LOD measurements were performed at low concentrations of nitro analytes. Fluorescencee responses of CPs 1 3 (3 mg dispersed in 3 ml of toluene) toward different concentrations of nitro analytes ( μm) in toluenee were recorded. LOD was determined usingg the equation: LOD = 3σ/m, where σ = standard deviation from ten blank measurements for the toluene suspensions of CPs 1 3 and m = slope of the linear curve plotted at lower concentration for LOD measurements. Blank readings #1 #2 #3 #4 #5 #6 #7 #8 #9 #10 Standard deviation (σ) Slope (m) R 2 LOD (3σ/m), μm (ppm) NB ) (0.41) 1,4 DNB (1.42) Nitro analyte 4 NT 2,4 DNT 2 NP 3 NP 4 NPP NM DMNB (1.59) (2.16) (1.60) (1.46) (1.84) (5.07) (9.87) Fig. S14 Linear region of fluorescence intensity for the toluene suspension of 1 upon incremental addition of nitro analytes in the range r from 10 μm to 100 μm. Thee following table lists the relevant parameters of LOD of the toluene suspension of 1 toward variouss nitro analytes. Conditions: λ em = 414 nm, λ ex = 280 nm. 15

17 Blank readings #1 #2 #3 #4 #5 #6 #7 #8 #9 #10 Standard deviation (σ) Slope (m) R 2 LOD (3σ/m), μm (ppm) NB ) (0.47) 1,4 DNB (1.29) Nitro analyte 4 NT 2,4 DNT 2 NP 3 NP 4 NPP NM (0.46) (1.05) 3.77 (0.52) 2.47 (0.34) (0.40) (3.43) DMNB (8.29) Fig. S15 Linear region of fluorescence intensity for the toluene suspension of 2 upon incremental addition of nitro analytes in the range r from 10 μm to 100 μm. Thee following table lists the relevant parameters of LOD of the toluene suspension of 2 toward variouss nitro analytes. Conditions: λ em = 466 nm, λ ex = 280 nm. 16

18 Blank readings #1 #2 #3 #4 #5 #6 #7 #8 #9 #10 Standard deviation (σ) Slope (m) R 2 LOD (3σ/m), μm (ppm) NB ) (0.63) 1,4 DNB (1.66) Nitro analyte 4 NT 2,4 DNT 2 NP 3 NP 4 NPP NM (4.42) DMNB (4.73) (2.35) (3.92) (3.82) (7.70) (6.79) Fig. S16 Linear region of fluorescence intensity for the toluene suspension of 3 upon incremental addition of nitro analytes in the range r from 10 μm to 100 μm. Thee following table lists the relevant parameters of LOD of the toluene suspension of 3 toward variouss nitro analytes. Conditions: λ em = 434 nm, λ ex = 280 nm. 17

19 Table S2. Comparison of sensing performances toward NB among various CP/MOF sensors CP/MOF based sensors K sv,m 1 LOD, μm (ppm) Media Reference [Zn 2 (1,4 bdc)(1,4 Hbdc) 2 (NI bpy 34) 2 ] (1) (0.41) toluene This work [Zn 2 (2,6 ndc)(2,6 Hndc) 2 (NI bpy 34) 2 ] H 2 O (2) (0.47) toluene This work [Zn(Hbtc)(NI bpy 34)(H 2 O)] H 2 O (3) (0.63) toluene This work {[Zn(IPA)(L 1 )]} n 1.87 x 10 3 N.A. H 2 O S1 {[Cd(IPA)(L 1 )]} n 1.36 x 10 3 N.A. H 2 O S1 [Zn 2 (L 2 )(bpy)(h 2 O) 2 ] (H 2 O) 3 (DMF) 2 N.A (5) CH 3 CN S2 [Zn 3 (L 3 ) 2 (L 4 )] N.A. 406 (50) DMF S3 [NH 2 (CH 3 ) 2 ] 2 [Cd 17 (L 5 ) 12 (μ 3 H 2 O) 4 (DMF) 2 (H 2 O) 2 ] solvent N.A (0.135) DMF S4 [Eu(HL 6 ) 3 (CH 3 OH) 2 ] n (6.03) CHCl 3 S5 [Tb(HL 6 ) 3 (CH 3 OH)(H 2 O)] n H 2 O (6.52) CHCl 3 S5 Abbreviations: NI bpy 34 = N (pyridin 3 yl) 4 (pyridin 4 yl) 1,8 naphthalimide; 1,4 H 2 bdc = benzene 1,4 dicarboxylic acid; 2,6 H 2 ndc = naphthalene 2,6 dicarboxylic acid; H 3 btc = benzene 1,3,5 tricarboxylic acid; H 2 IPA = isophthalic acid; L 1 = (E) N' (pyridin 3 ylmethylene)nicotinohydrazide; H 4 L 2 = bis (3,5 dicarboxyphenyl)terephthalamide; bpy = 4,4 bipyridine; H 3 L 3 = 4 [3 (4 carboxyphenoxy) 2 [(4 carboxyphenoxy)methyl] 2 methyl propoxy]benzoic acid; L 4 = 1,4 bis(1 imidazolyl)benzene; H 3 L 5 = 2,4,6 tris[1 (3 carboxylphenoxy)ylmethyl]mesitylene; H 2 L 6 = 3 (picolinamido)benzoic acid. References (S1) B. Parmar, Y. Rachuri, K. K. Bisht, R. Laiya and E. Suresh, Inorg. Chem., 2017, 56, (S2) G. Y. Wang, L. L. Yang, Y. Li, H. Song, W. J. Ruan, Z. Chang and X. H. Bu, Dalton Trans., 2013, 42, (S3) M. Guo and Z. M. Sun, J. Mater. Chem., 2012, 22, (S4) D. Tian, Y. Li, R. Y. Chen, Z. Chang, G. Y. Wang and X. H. Bu, J. Mater. Chem. A, 2014, 2, (S5) S. Srivastava, B. K. Gupta and R. Gupta, Cryst. Growth Des., 2017, 17,

20 Fig. S17 EDX spectrum of the Cu 2+ 2 exchanged greenish crystals of 3 obtained from a metal ion exchange process for approximate 7 days. Fig. S18 Time dependent optical images of 3 during the Cu 2+ ion exchange processs within 30 minutes, showing gradual change in crystal color and maintenance e in crystal morphology. 19