Europium Metal-Organic Frameworks as Recyclable and Selective Turn-off
Fluorescence Sensors for Aniline Detection
Hui-Jun Fenga,b, Ling Xua*, Bing Liuc, Huan Jiaoa*
Table S1. Crystal and structure refinement data for compounds 1-4.
Compounds 1 2 3 4Empirical formula C30H13ClEu2N2O12 C31H25ClEu2N2O12 C32H27N2O12ClEu2 C22H19ClEuN2O8
Fw 932.79 956.90 970.93 626.82Crystal system monoclinic monoclinic monoclinic monoclinicSpace group P21/c P21/c C2/c P21/na/Å 8.0451(5) 12.0317(3) 19.1758(6) 13.0533(4)b/Å 21.3785(12) 19.5150(5) 10.9867(3) 13.1471(3)c/Å 18.3326(10) 17.2834(4) 33.4105(12) 14.0537(4)β/° 90.035(5) 122.332(2) 103.273(3) 104.088(3)V/Å3 3153.1(3) 3428.96(15) 6850.9(4) 2339.26(12)Z 4 4 8 4Dc(Mg·m-3) 1.965 1.854 1.883 1.7797μ/mm-1 4.093 3.765 3.771 2.846F(000) 1784.0 1856.0 3776.0 1237.2Crystal size/mm3 0.20 × 0.10 × 0.10 0.12 × 0.1 × 0.04 0.4 × 0.3 × 0.2 0.50 × 0.40 × 0.302θ/° 6.94 to 50.04 6.86 to 50.06 6.98 to 50.04 6.8 to 50.06Reflections collected
16396 32194 32067 12986
Independent reflections
5496 [Rint = 0.0799, Rsigma = 0.1251]
6037 [Rint = 0.0246, Rsigma = 0.0172]
6013 [Rint = 0.0360, Rsigma = 0.0266]
4093 [Rint = 0.0413, Rsigma = 0.0720]
S 1.022 1.074 1.071 1.035Final R1, wR2 [I>2σ(I)]
R1 = 0.0792, wR2 = 0.2109
R1 = 0.0253, wR2 = 0.0605
R1 = 0.0384, wR2 = 0.0805
R1 = 0.0436, wR2 = 0.1149
R1, wR2 (all data) 0.0966, 0.2252 0.0313, 0.0644R1 = 0.0414, wR2 = 0.0818
0.0572, 0.1264
Δρmax/min /e·Ǻ-3 3.98/-3.28 1.55/-0.69 0.94/-1.46 2.35/-0.97
R1 = (Σ||Fo| - |Fc || / Σ |Fo|). wR2 = [Σ (w(Fo2 - Fc
2)2) / Σ (w |Fo2|2)]1/2
Table S2. Crystal and structure refinement data for compounds 5-7.
Compounds 5 6 7Empirical formula C9H5EuO6 C8H6ClEuO5 C32H28ClEu3O22
Fw 361.10 369.54 1255.87Crystal system monoclinic monoclinic orthorhombicSpace group P21/c P21/c Pccna/Å 10.6681(5) 10.8775(4) 18.1011(8)
1
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016
b/Å 12.9245(5) 12.9198(4) 19.3828(8)c/Å 6.8298(5) 7.1307(3) 10.2749(4)β/° 95.245(5) 103.352(4) 90.00V/Å3 937.75(9) 975.03(6) 3604.9(3)Z 4 4 4Dc(Mg·m-3) 2.5575 2.517 2.314μ/mm-1 6.698 6.702 5.324F(000) 680.4 696.0 2408.0Crystal size/mm3 0.20 × 0.10 × 0.10 0.15 × 0.15 × 0.12 0.20 × 0.20 × 0.102θ/° 7.38 to 50.04 6.98 to 50.06 8.2 to 50.06Reflections collected 10564 9137 17736
Independent reflections1634 [Rint = 0.0462, Rsigma = 0.0398]
1715 [Rint = 0.0469, Rsigma = 0.0289]
3130 [Rint = 0.0313, Rsigma = 0.0216]
S 1.028 1.032 1.041Final R1, wR2 [I>2σ(I)] 0.0483, 0.1185 0.0206, 0.0555 0.0530, 0.1603R1, wR2 (all data) 0.0524, 0.1227 0.0230, 0.0571 0.0573, 0.1641Δρmax/min /e·Ǻ-3 4.33/-2.26 0.93/-0.57 2.73/-1.11
R1 = (Σ||Fo| - |Fc || / Σ |Fo|). wR2 = [Σ (w(Fo2 - Fc
2)2) / Σ (w |Fo2|2)]1/2
2
Table S3. Selected bond distances (Å) and bond angles (º) of compounds 1-4.
1 2 3 4Eu1-Cl1=2.761(4) Eu1-Cl1=2.8587(9) Eu1-Cl1=2.8269(15) Eu1-Cl1=2.9452(16)Eu1-O11=2.308(12) Eu1-O111=2.296(3) Eu1-O11=2.391(5) Eu1-O11=2.387(5)Eu1-O131=2.276(10) Eu1-O14=2.348(3) Eu1-O21=2.319(5) Eu1-O121=2.373(5)Eu1-O21=2.741(11) Eu1-O212=2.390(3) Eu1-O232=2.333(5) Eu1-O132=2.438(5)Eu1-O22=2.401(11) Eu1-O222=2.816(3) Eu1-O243=2.326(5) Eu1-O143=2.367(5)Eu1-O31=2.274(11) Eu1-O24=2.386(3) Eu1-O31=2.351(5) Eu1-O142=2.645(5)Eu1-O41=2.527(9) Eu1-O31=2.326(3) Eu1-O324=2.312(5) Eu1-O21=2.597(5)Eu1-O42=2.457(10) Eu1-O42=2.349(3) Eu2-Cl1=2.8141(15) Eu1-O31=2.530(5)Eu2-Cl1=2.907(4) Eu2-Cl13=2.8556(9) Eu2-O12=2.327(5) Eu1-O32=2.424(5)Eu2-O122=2.298(11) Eu2-O124=2.339(3) Eu2-O136=2.579(4)Eu2-O141=2.362(12) Eu2-O13=2.349(3) Eu2-O134=2.444(4)Eu2-O21=2.369(11) Eu2-O222=2.359(3) Eu2-O146=2.502(5)Eu2-O233=2.424(10) Eu2-O23=2.482(3) Eu2-O22=2.342(4)Eu2-O243=2.552(10) Eu2-O24=2.631(3) Eu2-O41=2.323(4)Eu2-O322=2.418(14) Eu2-O323=2.327(3) Eu2-O425=2.381(4)Eu2-O412=2.441(10) Eu2-O41=2.387(3)
Cl1-Eu1-Eu2=44.58(8) Cl1-Eu1-Eu2=137.27(2) Cl1-Eu1-Eu11=129.11(3) O11-Eu1-Cl1=144.98(13)O11-Eu1-Eu2=86.5(3) O112-Eu1-Eu2=115.45(8) O11-Eu1-Eu11=135.46(12) O121-Eu1-Cl1=75.12(13)O11-Eu1-Cl1=85.9(4) O112-Eu1-Cl1=82.68(8) O11-Eu1-Cl1=82.11(13) O121-Eu1-O11=134.31(18)O11-Eu1-O21=72.2(4) O112-Eu1-O14=89.98(12) O21-Eu1-Eu11=126.64(12) O132-Eu1-Cl1=78.66(14)O11-Eu1-O22=81.0(5) O112-Eu1-O211=158.41(12) O21-Eu1-Cl1=80.32(12) O132-Eu1-O11=85.7(2)O11-Eu1-O41=75.0(4) O112-Eu1-O221=149.51(10) O21-Eu1-O11=84.32(18) O132-Eu1-O121=83.81(19)O11-Eu1-O42=123.6(4) O112-Eu1-O24=77.67(11) O21-Eu1-O232=77.66(18) O142-Eu1-Cl1=118.91(11)O131-Eu1-Eu2=63.2(3) O112-Eu1-O31=79.80(14) O21-Eu1-O243=144.31(19) O143-Eu1-Cl1=142.23(13)O131-Eu1-Cl1=80.1(3) O112-Eu1-O42=109.33(12) O21-Eu1-O31=142.3(2) O143-Eu1-O11=72.03(18)O131-Eu1-O11=147.8(4) O14-Eu1-Eu2=68.96(7) O232-Eu1-Eu11=65.97(13) O142-Eu1-O11=70.93(17)
3
O131-Eu1-O21=76.1(4) O14-Eu1-Cl1=153.11(8) O232-Eu1-Cl1=157.96(14) O142-Eu1-O121=67.91(17)O131-Eu1-O22=82.7(4) O14-Eu1-O211=87.88(13) O232-Eu1-O11=96.51(18) O143-Eu1-O121=77.01(18)O131-Eu1-O41=134.4(3) O14-Eu1-O221=73.57(10) O232-Eu1-O31=74.8(2) O143-Eu1-O132=122.91(17)O131-Eu1-O42=82.2(4) O14-Eu1-O24=74.61(11) O243-Eu1-Eu11=57.34(13) O142-Eu1-O132=51.21(16)O21-Eu1-Eu2=33.1(2) O14-Eu1-O42=133.97(10) O243-Eu1-Cl1=76.01(14) O21-Eu1-Cl1=77.41(13)O21-Eu1-Cl1=74.6(2) O211-Eu1-Eu2=83.70(8) O243-Eu1-O11=117.87(18) O21-Eu1-O11=124.81(19)O22-Eu1-Eu2=79.6(3) O211-Eu1-Cl1=89.59(9) O243-Eu1-O232=122.81(18) O21-Eu1-O121=71.44(18)O22-Eu1-Cl1=123.3(3) O211-Eu1-O221=48.89(10) O243-Eu1-O31=73.3(2) O21-Eu1-O132=149.15(19)O22-Eu1-O21=48.9(4) O221-Eu1-Eu2=34.83(6) O31-Eu1-Eu11=62.25(14) O21-Eu1-O143=69.85(18)O22-Eu1-O41=134.2(3) O221-Eu1-Cl1=123.03(7) O31-Eu1-Cl1=125.12(16) O21-Eu1-O142=128.81(17)O22-Eu1-O42=149.9(4) O24-Eu1-Eu2=38.51(7) O31-Eu1-O11=73.87(19) O31-Eu1-Cl1=74.99(12)O31-Eu1-Eu2=146.2(3) O24-Eu1-Cl1=128.12(8) O324-Eu1-Eu11=61.93(15) O31-Eu1-O11=70.95(18)O31-Eu1-Cl1=157.0(4) O24-Eu1-O211=122.20(11) O324-Eu1-Cl1=91.44(15) O31-Eu1-O121=146.78(17)O31-Eu1-O11=111.7(5) O24-Eu1-O221=73.32(9) O324-Eu1-O11=160.32(19) O31-Eu1-O132=76.43(17)O31-Eu1-O131=90.8(5) O31-Eu1-Eu2=141.05(8) O324-Eu1-O21=76.25(19) O31-Eu1-O143=136.21(17)O31-Eu1-O21=123.9(4) O31-Eu1-Cl1=77.45(9) O324-Eu1-O232=82.53(19) O31-Eu1-O142=115.88(16)O31-Eu1-O22=75.7(4) O31-Eu1-O14=75.80(11) O324-Eu1-O243=78.02(19) O31-Eu1-O21=115.22(18)O31-Eu1-O41=77.8(4) O31-Eu1-O211=78.85(14) O324-Eu1-O31=124.2(2) O32-Eu1-Cl1=91.38(14)O31-Eu1-O42=78.7(4) O31-Eu1-O221=118.98(11) Cl1-Eu2-Eu25=143.53(3) O32-Eu1-O11=74.29(19)O41-Eu1-Eu2=135.7(2) O31-Eu1-O24=142.49(13) O12-Eu2-Eu25=127.38(12) O32-Eu1-O121=142.24(19)O41-Eu1-Cl1=93.5(2) O31-Eu1-O42=146.94(12) O12-Eu2-Cl1=82.01(13) O32-Eu1-O132=128.62(17)O41-Eu1-O21=145.7(3) O42-Eu1-Eu2=65.01(7) O12-Eu2-O136=97.46(15) O32-Eu1-O142=145.13(18)O42-Eu1-Eu2=115.8(3) O42-Eu1-Cl1=72.56(8) O12-Eu2-O134=146.78(17) O32-Eu1-O143=95.35(17)O42-Eu1-Cl1=79.2(3) O42-Eu1-O211=87.25(13) O12-Eu2-O146=73.11(17) O32-Eu1-O21=71.24(18)O42-Eu1-O21=148.3(3) O42-Eu1-O221=69.04(10) O12-Eu2-O22=89.08(18) O32-Eu1-O31=52.44(17)O42-Eu1-O41=52.3(3) O42-Eu1-O24=69.75(11) O12-Eu2-O425=72.69(17)Cl1-Eu1-Eu12=138.54(9) Cl13-Eu2-Eu1=131.18(2) O136-Eu2-Eu25=37.51(10)Cl1-Eu2-Eu1=41.81(7) O124-Eu2-Eu1=139.44(8) O134-Eu2-Eu25=39.98(10)O122-Eu2-Eu1=140.6(3) O124-Eu2-Cl13=86.70(8) O134-Eu2-Cl1=125.97(11)O122-Eu1-Eu12=60.7(3) O124-Eu2-O13=133.92(12) O136-Eu2-Cl1=131.71(11)
4
O122-Eu1-Cl1=149.0(3) O124-Eu2-O221=151.47(12) O134-Eu2-O136=77.49(16)O122-Eu1-O141=137.8(4) O124-Eu2-O23=71.51(12) O134-Eu2-O146=122.55(15)O122-Eu1-O21=102.6(4) O124-Eu2-O24=110.34(11) O146-Eu2-Eu25=85.67(11)O122-Eu1-O233=79.2(4) O124-Eu2-O41=78.61(11) O146-Eu2-Cl1=83.42(11)O122-Eu1-O243=76.5(4) O13-Eu2-Eu1-65.33(7) O146-Eu2-O136=51.35(14)O122-Eu1-O322=72.7(5) O13-Eu2-Cl13=69.88(8) O22-Eu2-Eu25=114.55(12)O122-Eu1-O412=82.3(4) O13-Eu2-O221=74.60(11) O22-Eu2-Cl1=83.06(12)O141-Eu2-Eu1=66.9(3) O13-Eu2-O23=76.06(13) O22-Eu2-O134=78.49(16)O141-Eu1-Eu12=82.3(3) O13-Eu2-O24=69.36(11) O22-Eu2-O136=145.14(16)O141-Eu1-Cl1=72.9(3) O13-Eu2-O41=133.65(10) O22-Eu2-O146=158.96(17)O141-Eu1-O21=89.4(4) O221-Eu2-Eu1-42.97(8) O22-Eu2-C186=163.54(18)O141-Eu1-O233=124.4(5) O221-Eu2-Cl13=107.09(8) O22-Eu2-O425=78.07(17)O141-Eu1-O243=145.6(4) O221-Eu2-O23=126.40(11) O41-Eu2-Eu25=69.62(11)O141-Eu1-O322=70.9(5) O221-Eu2-O24=77.33(10) O41-Eu2-Cl1=73.99(12)O141-Eu1-O412=74.8(4) O221-Eu2-O41=79.34(11) O41-Eu2-O12=142.62(18)O21-Eu2-Eu1=39.2(3) O23-Eu2-Eu1=84.01(7) O41-Eu2-O134=69.35(16)O21-Eu1-Eu12=135.7(3) O23-Eu2-Cl13=103.39(9) O41-Eu2-O136=78.76(16)O21-Eu1-Cl1=77.6(3) O23-Eu2-O24=50.50(10) O41-Eu2-O146=75.99(18)O21-Eu1-O233=127.5(4) O24-Eu2-Eu1-34.38(7) O41-Eu2-O22=115.32(18)O21-Eu1-O243=76.5(4) O24-Eu2-Cl13=135.91(7) O41-Eu2-O425=137.19(16)O21-Eu1-O322=77.3(5) O323-Eu2-Eu1=118.84(8) O425-Eu2-Eu25=67.99(11)O21-Eu1-O412=160.3(4) O323-Eu2-Cl13=78.77(9) O425-Eu2-Cl1=148.44(12)O233-Eu1-Eu12=91.6(2) O323-Eu2-O124=77.07(13) O425-Eu2-O134=74.62(16)O233-Eu2-Eu1=113.9(2) O323-Eu2-O13=131.94(13) O425-Eu2-O136=71.44(15)O233-Eu1-Cl1=76.7(3) O323-Eu2-O221=81.24(12) O425-Eu2-O146=106.20(17)O233-Eu1-O243=52.6(3) O323-Eu2-O23=148.26(12) Eu2-Cl1-Eu1=107.54(5)O233-Eu1-O412=72.0(3) O323-Eu2-O24=143.43(11)O243-Eu1-Eu12=129.3(3) O323-Eu2-O41=79.28(12)O243-Eu2-Eu1=83.2(3) O41-Eu2-Eu1=69.40(7)O243-Eu1-Cl1=73.5(3) O41-Eu2-Cl13=155.82(8)
5
O322-Eu1-Eu12=58.9(4) O41-Eu2-O23=90.13(12)O322-Eu2-Eu1-99.4(4) O41-Eu2-O24=67.91(11)O322-Eu1-Cl1=135.6(4) Eu25-Cl1-Eu1=111.73(3)O322-Eu1-O233=146.5(5)O322-Eu1-O243=133.4(5)O322-Eu1-O412=86.3(5)O412-Eu2-Eu1=136.5(2)O412-Eu1-Eu12=31.9(2)O412-Eu1-Cl1=108.0(2)O412-Eu1-O243=123.2(3)Eu1-Cl1-Eu1=93.62(11)Symmetry codes: 1) 1-X,-1/2+Y,1/2-Z; 2-1+X,+Y,+Z; 3+X,3/2-Y,1/2+Z. 2) 11+X,-1/2-Y,1/2+Z; 2-1-X,-1-Y,1-Z; 3+X,-1/2-Y,1/2+Z; 4-1-X,1/2+Y,3/2-Z. 3) 1-X,+Y,1/2-Z; 21/2-X,1/2+Y,1/2-Z; 3-1/2+X,1/2+Y,+Z; 4+X,-1+Y,+Z; 5-X,-Y,-Z; 6-X,1-Y,-Z. 4) 11-X,-Y,2-Z; 21/2+X,-1/2-Y,1/2+Z; 31/2-X,1/2+Y,3/2-Z.
Table S4. Selected bond distances (Å) and bond angles (º) of compounds 5-7.
5 6 7Eu1-O111=2.284(8) Eu1-Cl1=2.7788(10) Eu1-O11=2.375(8)Eu1-O122=2.342(7) Eu1-Cl11=2.8253(10) Eu1-O122=2.310(8)Eu1-O133=2.327(8) Eu1-O11=2.346(3) Eu1-O21=2.511(8)Eu1-O14=2.350(8) Eu1-O122=2.289(3) Eu1-O1W=2.474(8)Eu1-C1=2.959(13) Eu1-O133=2.333(3) Eu2-Cl1=2.876(6)Eu1-O14=2.479(8) Eu1-O144=2.258(3) Eu2-O134=2.323(8)Eu1-O1=2.572(9) Eu1-O1W=2.409(3) Eu2-O145=2.295(8)Eu1-O2=2.588(9) O12-Eu11=2.289(3) Eu2-O22=2.438(8)Eu1-O23=2.394(8) Eu2-O236=2.316(8)
Cl1-Eu1-Cl11=82.01(2) Eu2-O245=2.326(7)O121-Eu1-O112=77.8(3) O11-Eu1-Cl11=86.16(7) Eu2-O2W=2.546(9)O133-Eu1-O112=100.2(3) O11-Eu1-Cl1=92.58(8) Eu2-O3W=2.519(8)O133-Eu1-O121=76.6(3) O11-Eu1-O1W=122.25(11)
6
O14-Eu1-O112=101.1(3) O122-Eu1-Cl11=152.27(7) O11-Eu1-O111=107.2(4)O14-Eu1-O121=145.3(3) O122-Eu1-Cl1=76.97(7) O111-Eu1-O21=142.2(3)O14-Eu1-O133=136.3(3) O122-Eu1-O11=77.02(10) O11-Eu1-O21=71.8(3)C1-Eu1-O112=175.4(3) O122-Eu1-O133=116.29(10) O11-Eu1-O211=142.2(3)C1-Eu1-O121=101.9(3) O122-Eu1-O1W=69.98(10) O11-Eu1-O1W1=67.5(3)C1-Eu1-O133=75.3(3) O133-Eu1-Cl11=75.10(7) O11-Eu1-O1W=79.2(3)C1-Eu1-O14=81.8(3) O133-Eu1-Cl1=76.19(8) O111-Eu1-O1W=67.5(3)O14-Eu1-O112=76.6(3) O133-Eu1-O11=159.20(10) O122-Eu1-O11=140.9(3)O1-Eu1-O112=156.9(3) O133-Eu1-O1W=78.37(11) O123-Eu1-O11=93.6(3)O14-Eu1-O121=75.0(3) O144-Eu1-Cl11=79.27(8) O123-Eu1-O122=90.0(4)O1-Eu1-O121=80.6(3) O144-Eu1-Cl1=161.10(8) O122-Eu1-O21=71.5(3)O1-Eu1-O133=82.7(3) O144-Eu1-O11=83.66(11) O123-Eu1-O21=75.4(3)O14-Eu1-O133=151.5(3) O144-Eu1-O122=119.78(11) O122-Eu1-O1W=78.9(3)O14-Eu1-O14=71.1(3) O144-Eu1-O133=101.26(11) O123-Eu1-O1W=150.8(3)O1-Eu1-O14=91.8(3) O144-Eu1-O1W=74.12(11) O236-Eu2-O3W=80.1(3)O14-Eu1-C1=107.9(3) O1W-Eu1-Cl1=122.69(8) O245-Eu2-Cl1=72.4(2)O1-Eu1-C1=24.9(3) O1W-Eu1-Cl11=137.55(8) O245-Eu2-O22=76.3(3)O2-Eu1-O112=152.8(3) Eu1-Cl1-Eu12=119.37(4) O245-Eu2-O2W=142.9(3)O23-Eu1-O112=78.5(3) O245-Eu2-O3W=73.9(3)O2-Eu1-O121=123.1(3) O2W-Eu2-Cl1=70.7(2)O23-Eu1-O121=135.8(3) O3W-Eu2-Cl1=128.4(2)O2-Eu1-O133=71.7(3) O3W-Eu2-O2W=129.0(3)O23-Eu1-O133=71.5(3)O23-Eu1-O14=76.0(3)O2-Eu1-O14=71.9(3)O23-Eu1-C1=98.8(3)O2-Eu1-C1=25.0(3)O23-Eu1-O1=123.6(3)O2-Eu1-O14=122.9(3)O23-Eu1-O14=133.5(3)
7
O2-Eu1-O1=49.9(3)Symmetry codes: 5) 1-1+X,1/2-Y,-1/2+Z; 2-1+X,+Y,+Z; 31-X,1-Y,1-Z; 4+X,1/2-Y,1/2+Z. 6) 1+X,3/2-Y,-1/2+Z; 2+X,3/2-Y,1/2+Z; 31+X,3/2-Y,1/2+Z; 4-X,1/2+Y,-1/2-Z. 7) 11/2-X,1/2-Y,+Z; 2+X,1/2-Y,1/2+Z; 31/2-X,+Y,1/2+Z; 41-X,-Y,-Z; 51-X,1/2+Y,1/2-Z; 61-X,-Y,1-Z.
8
O O
O O
EuEu
EuEu
O O
O O
EuEu
Eu
O O
O O
EuEu
EuEu
O O
O O
Eu
Eu
O OH
OH O
Eu
Eu
O O
O O
EuEu
Eu Eu
(a) (b) (c) (d) (e) (f)
Scheme S1. The coordination fashions of BDC2− ligands in compounds 1-7.
(1) (2)
(3) (4)
(5) (6)
9
(7)
Fig. S1. The coordination spheres of Eu(III) centers in compounds 1-7.
(a) (b)
Fig. S2. The 2D layers of compound 1 along the ab-plane (a) or the ac-plane (b).
(a) (b) (c)
Fig. S3. The 2D layers of compound 2.
10
(a) (b) (c)
Fig. S4. The 1D chain (a) and 2D layers (b, c) of compound 3.
(a) (b)
Fig. S5. The (3,6) layer of compound 4 (a) and 2D layer of compound 5 (b).
(a) (b)
Fig. S6. The 2D layer of compound 6(a) and the topological 2D layer of compound 7 (b).
11
0 10 20 30 40 50 602
Inte
nsity
Simulated Experimental
Compound 1
0 10 20 30 40 50 60
Inte
nsity
2
Compound 2 Simulated Experimental
0 10 20 30 40 50 60
Compound 3
2
Simulated Experimental
Inte
nsity
0 10 20 30 40 50 60
Compound 4 Simulated Experimental
2
Inte
nsity
0 10 20 30 40 50 60
Compound 5 Simulated Experimental
Inte
nsity
2
0 10 20 30 40 50 60
Compound 6
Inte
nsity
2
Simulated Experimental
0 10 20 30 40 50 60
Compound 7 Simulated Experimental
Inte
nsity
2
Fig. S7. Comparison of X-ray powder diffraction patterns of compounds 1-7 to those simulated
12
from single crystal structure data.
Table S5. The main IR characteristic absorption peaks for compounds 1-7.
compounds υas(COO–)/cm-1 υs(COO–)/cm-1 δ(C–H)(MI)/cm-1 δ(C–N)(MI)/cm-1 δ(C–H)/cm-
1
1 1625, 1596 1504, 1404 3153, 3103 1168 2979, 2928
2 1610, 1546 1504. 1386 3168,3062 1172 2993, 2949
3 1610, 1587 1506, 1396 3145, 3105 1164 3020, 2949
4 1616,1589 1504, 1396 3161, 3111 1174 2965, 2954
5 1633,1591 1506,1404 2970,2956
6 1630,1592 1504,1404 2995,2950
7 1635,1596 1510,1406 2980,2936
0 100 200 300 400 500 600 700 800
0
20
40
60
80
100
Compound 3
Compound 2
270C300C
Compound 1
350C
W%
T (C)
(a)
0 100 200 300 400 500 600 700 800
40
50
60
70
80
90
100
T (oC)
W%
560oC
450oC
280oC
(b)
0 100 200 300 400 500 600 700 80030
40
50
60
70
80
90
100
T (oC)
W%560oC
390oC
250oC
(c)
0 100 200 300 400 500 600 700 800
60
65
70
75
80
85
90
95
100
105
260oC
540oC
W%
T (oC)
(d)
13
0 100 200 300 400 500 600 700 80060
65
70
75
80
85
90
95
100
105
T (oC)
W%
150oC
510oC
(e)
Fig. S8. TG curves of compounds 1-3 (a), 4 (b), 5 (c), 6 (d), 7 (e).
Fig. S9. Temperature-dependent emission intensities for compounds 1, 4, 6 and 7.
14
Fig. S10. Suspension-state photoluminescent spectra of 5D0→7F2 at 615 nm for compound 4
dispersed in aniline and contrast organic amines and alkylbenzene DMF solutions.
200 250 300 350 400 450 (nm)
Abs
Compound 4 Compound 6 Methylbenzene Ethylbenzene Ethylbenzene Methylamine n-butylamine Ethylenediamine Triethanolamine DMF Aniline
Fig. S11. UV-Vis spectra of compounds 4 and 6, aniline, the contrast organic amides and
alkylbenzenes.15
200 250 300 350 400 450 500
Inte
nsity
(nm)
H2BDC H2BDC added aniline Aniline
Fig. S12. Emission spectra of free H2BDC, free aniline and the mixture of H2BDC and aniline.
Fig. S13. The concentration-dependent fluorescence quenching of aniline mixed with compound 4
in DMF suspension solutions.
16
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2
0
1000
2000
3000
4000
5000
6000
Inte
nsity
-lg c/M
Fig. S14. The luminescence intensity of compound 4 vs. aniline concentration in water solution.
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2
0
1000
2000
3000
4000
5000
6000
Inte
nsity
-lg c/M
Fig. S15. The luminescence intensity of compound 4 vs. aniline concentration in DMF solution.
17
Fig. S16. Suspension-state photoluminescent spectra of 5D0→7F2 at 615 nm for compound 6
dispersed in aniline and contrast organic amines and alkylbenzene aqueous solutions.
Fig. S17. Suspension-state photoluminescent spectra of 5D0→7F2 at 615 nm for compound 6
dispersed in aniline and contrast organic amines and alkylbenzene DMF solutions.18
Fig. S18. The comparison of fluorescence intensities of 5D0→7F2 emissions at 615 nm for
compound 6 dispersed in aniline mixed with contrast organic amines and alkylbenzene samples.
Fig. S19. The comparison of fluorescence intensities of 5D0→7F2 emissions at 615 nm for ten
recycling times that compound 6 detects aniline.
19
Fig. S20. The concentration-dependent fluorescence quenching of aniline mixed with compound 6
in water suspension solutions.
Fig. S21. The concentration-dependent fluorescence quenching of aniline mixed with compound 6
in DMF suspension solutions.
20
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4
0
1000
2000
3000
4000
5000
6000
-lg c/M
Inte
nsity
Fig. S22. The luminescence intensity of compound 6 vs. aniline concentration in water solution.
2.0 2.5 3.0 3.5 4.0 4.5 5.0
0
500
1000
1500
2000
2500
3000
-lg c/M
Inte
nsity
Fig. S23. The luminescence intensity of compound 6 vs. aniline concentration in DMF solution.
21
