Supplementary Information

Multifunctional anionic indium-organic frameworks for organic dyes

separation, white-light emission and dual-emitting Fe3+ sensing

Yu-Hui Luo,ab A-Di Xie,a Wen-Cheng Chen,*b Dong Shen,b Dong-En Zhang,*a Zhi-Wei Tong,a and Chun-Sing Lee*b

a Department of Chemical Engineering, Jiangsu Ocean University, Lianyungang 222000, P. R. Chinab Center of Super-Diamond and Advanced Films (COSDAF) and Department of Chemistry, City University of Hong Kong, Hong Kong SAR, P. R. China

Materials and MeasurementsAll reagents and solvents were purchased from commercial sources and used without

further purification. Powder X-ray diffraction (PXRD) patterns were collected on a Bruker D2 X-ray diffractometer with graphite monochromatized Cu Kα radiation (λ = 0.15418 nm) and 2θ ranging from 6 to 50 ° with an increment of 0.02 ° and a scanning rate of 5 °/min. The FT-IR spectrum was measured in KBr pellets in the range 4000-400 cm-1 on a Mattson Alpha-Centauri spectrometer. The UV-Vis absorption was measured with a Cary 500 UV-Vis-NIR Spectrophotometer. The fluorescent spectroscopy was measured on a FLS980 Edinburgh Luminescence Spectrometer at room temperature with a light source of Xenon lamp.X-ray crystallography

Crystallographic diffraction date for compound 1 was recorded on a Bruker Apex CCD diffractometer with graphite monochromatized Mo-Kα radiation (λ = 0.71073 Å) at 293k. The structure was solved by Direct Method of SHELXS and refined by full-matrix least-squares techniques by using the SHELXL-2014 program.1 All non-hydrogen atoms were refined with anisotropic temperature parameters. All hydrogen atoms were placed in geometrically idealized position as a riding mode. The solvent molecules and [Me2NH2]+ cations in the crystal are highly disordered and are removed by using the SQUEEZE routine of PLATON.2 ISOR command was used to restrict O3

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2019

and C8 for ADP alert. The crystallographic data for 1 is summarized in Table S1, and the selected bond lengths and angles are listed in Table S2. CCDC number for compound 1 is 1954105.

Table S1. Crystal data and structure refinements for 1.

Compounds 1Formula C18H14InN3O8

Fw 515.14Temp (K) 293(2)Wavelength (Å) 0.71073Crystal system TetragonalSpace group P432 2a = b (Å) 9.9792(16)c (Å) 43.855(14)α = β = γ (deg) 90V (Å3) 4367(2)Z 4Reflns coll./unique 3964/21900F000 1024.0Density (g cm-3) 0.783Mu (mm-1) 0.565Rint 0.1139GOF 0.997R1, wR2 [I>2σ(I)]a 0.0538, 0.1447R1, wR2 (all data)a 0.0797, 0.1545

aR1 = ∑||F0| – |Fc||/∑|F0|; wR2 = ∑[w(F02 – Fc2)2]/∑[w(F0

2)2]1/2.

Table S2. Selected bond lengths (Å) and angles (o) for 1.a

In1-O1 2.178(6) In1-O2 2.484(6)In1-O1#1 2.178(6) In1-O2#1 2.484(6)In1-O3 2.378(7) In1-O4 2.219(5)In1-O3#1 2.378(7) In1-O4#1 2.219(5)O1-In1-O1#1 126.4(5) O3#3-In1-O3#2 93.9(5)O1-In1-O4#2 81.8(2) O1-In1-O2#1 87.8(3)O1#1-In1-O4#2 123.0(3) O1#1-In1-O2#1 54.8(2)O1-In1-O4#3 123.0(3) O4#2-In1-O2#1 83.2(3)O1#1-In1-O4#3 81.8(2) O4#3-In1-O2#1 136.6(2)O4#2-In1-O4#3 127.0(3) O3#3-In1-O2#1 168.1(2)O1-In1-O3#3 137.1(2) O3#2-In1-O2#1 87.3(4)O1#1-In1-O3#3 83.3(4) O1-In1-O2 54.8(2)O4#2-In1-O3#3 87.7(3) O1#1-In1-O2 87.8(3)O4#3-In1-O3#3 55.3(2) O4#2-In1-O2 136.6(2)O1-In1-O3#2 137.1(2) O4#3-In1-O2 83.2(3)

O1#1-In1-O3#2 83.3(4) O3#3-In1-O2 87.3(4)O4#2-In1-O3#2 55.3(2) O3#2-In1-O2 168.1(2)O4#3-In1-O3#2 87.7(3) O2#1-In1-O2 94.0(5)

a #1 y, x, 1/4-z; #2 y, 1+x, 1/4-z; #3 1+x, y, z; #4 -1+x, y, z.

Fig. S1. PXRD patters of compound 1 (left) and 2 (right) under different conditions.

Fig. S2. Structures of organic dyes used in this work.

Fig. S3. Temporal evolution of UV-Vis absorption spectra of dyes in DMF solution in the presence of compound 1.

Fig. S4. (a) Optical microscopy of BG@1 crystals. (b) Optical microscopy of crushed BG@1 crystals. (c) EDX result of BG@1 crystal. (d) EDX result of BG@1 crystal after releasing BG+ in NaNO3 solution.

Table S3 Comparison of MB adsorption capacity in MOF materials.Materials Adsorption capacity (mg g-1) Ref.LIFM-WZ-4 1492 31 714 4PW11V@MIL-101 371 5Cd-MOF (2) 317.9 6Compound 1 284.2 This workCompound 2 158.7 This workActivated carbon 135 7Zn-DDQ 135 8Cu-DDQ 90 8Pb-DDQ 86 8NENU-505 33.5 9Cd-MOF (3) 30 6MOF@graphite oxide 18 10

446-MOF 17 11

Fig. S5. (a) BG, (b) MB, (c) R6G, and (d) SO gradually released from dye@1 in the presence of Na+. Insert: The release kinetic curves of dye@1 in a saturated NaNO3 solution of DMF.

Fig. S6. (a)-(f) respectively represent the UV-Vis absorption spectra of equimolar BG/MO, BG/CR, BG/DY, BG/SDIII, BG/R6G, and BG/SO in the presence of compound 1.

Fig. S7. Temporal evolution of UV-Vis absorption spectra of dyes in DMF solution in the presence of compound 2.

Fig. S8. The adsorption kinetic curves of compound 2.

Fig. S9. (a)-(f) respectively represent the UV-Vis absorption spectra of equimolar BG/MO, BG/CR, BG/DY, BG/SDIII, BG/R6G, and BG/SO in the presence of compound 2.

Fig. S10. Temporal evolution of UV-Vis absorption spectra of R6G in DMF solution in the presence of compound 2.

Fig. S11. Representation of the size of BG, MB, R6G and SO.

The order of molecular size is R6G > BG ≈ SO > MB. As shown in Fig. S3 and Fig.

S9, compound 1 can absorb R6G while compound 2 does not absorb R6G at all. This

is because the pore size of compound 2 is too small to let R6G absorb in.

Fig. S12. PXRD patters of (a) compound 1; and (b) compound 2 after loading dyes.

Fig. S13. The emission spectrum of compound 2 and the absorption spectrum of SO in DMF.

Fig. S14. (a) Solid-state emission spectra of compound 2 and free H4bptc ligand. (b) Emission spectrum of SO in DMF.

Fig. S15. Solid-state emission spectra of compound 1 and free H4abtc ligand at room temperature. The peak at 520 nm is the frequency-doubled reflection peak of the 260 nm excitation light.

Fig. S16. Emission spectra of compound 1 in DMF solution at room temperature.

Fig. S17. Emission spectra of compound 1 in DMF solution in the presence of different metal ions.

Fig. S18. Emission spectra of compound 1 in DMF solution with different concentration of Fe3+.

Fig. S19. Emission spectra of compound 2 in DMF solution in the presence of different metal ions. The sensing of complex 2 on metal ions exhibits low selectivity.

Table S4 Comparison of reported MOF sensors for Fe3+ ion detection.a

MOFs KSV (M−1)Detection

limit (M)Medium Ref.

Compound 1 3497.3 3.45 × 10-5 DMF This work

Pt+@[Me2NH2]2[Zn5(H2O)2(L1)6]·32

DMF

- 7.7 × 10-6 MeOH 12

PAF-5CF 11865 3.8 × 10-5 EtOH 13Ru2+@[Me2NH2]2[Zn5(H2O)2(L1)6]·

32DMF

- 2.7 × 10-5 MeOH 12

FJI-C8 8245 2.33 × 10-5 DMF 14

[Eu2(ppda)2(npdc)(H2O)2]n 1.64 × 105 1.66 × 10-5 H2O 15

Dye@Bio-MOF-1 5072 - DMF 16

Tb-DSOA 3543 - DMF 17

{[Cd2(bptc)(2,2′-bipy)2(H2O)2]}n 8610 - DMF 18[Zn3(L2)2(bipy)(μ3-OH)2]·3H2O 2.3 × 104 DMF 19CSMCRI-1 2.54 × 104 - DMF 20H3O[In3(dcpy)4(OH)2]·3DMF·4H2O 4300 - H2O 21{(Me2NH2)[Tb(OBA)2]·(Hatz)·(H2O

)1.5}n3.4 × 104 - H2O 22

a H2ppda = 4-(pyridin-3-yloxy)-phthalic acid; H2npdc = naphthalene-1,4-dicarboxylic

acid; L1 = 4‐(5,7‐dioxo‐5,7‐dihydroimidazo[4,5‐f]isoindol‐6(1H)‐yl) benzoic acid;

Hatz = 3-amino-1,2,4-triazole; bipy = 4,4′-bipyridine; H2L2 = 9H-carbazolyl-3,6-

dicarboxylic acid; bptc = biphenyl-3,3’,5,5’-tetracarboxylic acid; dcpy = 3-(2′,5′-

dicarboxylphenyl)pyridine acid.

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