Supporting Information Strongly Fluorescent Hydrogel as a Blue-Emitting anomaterial: An Approach toward Understanding Fluorescence-Structure Relationship Tae Ho Kim, Joobeom Seo, Soo Jin Lee, Shim Sung Lee, Jineun Kim, and Jong Hwa Jung* Department of Chemistry and Research Institute of atural Science, Gyeongsang ational University, Jinju 660-701, Korea Table of Contents: Title and table of contents S1 Experimental Section S2-S5 Figure S1. Differential scanning calorimetry curves of hydrogel 1 at ph 7. S6 Figure S2. Fluorescence spectra of the hydrogel 1 (0.1 wt%) prepared at different ph vlaues S7 Table S1. Crystal and experimental data S8 Figure S3. Molecular structure of 1 (ph 7). S9 Figure S4. Packing structure of 1 (ph 7). S9 Figure S5. Representation of intermolecular hydrogen bonds of 1 (ph 7) S10 Table S2. Intermolecular hydrogen bonds geometry for 1 S10 Figure S6. Molecular structure of 1 2HO 3 S11 Figure S7. Representation of intermolecular hydrogen bonds of 1 2HO 3 S11 Table S3. Intermolecular hydrogen bonds geometry for 1 2HO 3 S12 Figure S8. Molecular structure of 2 S13 Figure S9. Packing structure of 2 S14 Figure S10. Representation of intermolecular hydrogen bonds (dashed lines) and - stacking interactions (dashed arrows) of 2 S15 Table S4 Intermolecular hydrogen bonds geometry (Å, º) for 2 S15 References S16 S1
Experimental Section General Method: The FT-IR spectra of the compounds were measured with a Shimadzu FTIR-8400S spectrometer. Steady-state luminescence spectra were acquired with a Perkin Elmer LS 50B spectrophotometer. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were performed under 2 (g) at a scan rate of 10 C min -1 using a TA SDT Q600 thermal analyzer. Differential scanning calorimetry (DSC) were performed under 2 (g) at a scan rate of 1 C min -1 using a TA Q200 thermal analyzer system, T g was taken at the middle of the step transition in the second heating run. For field emission scanning electron microscope (FE-SEM) a piece of compounds was placed on a carbon tape after gold coating, the specimen was then examined with JEOL JEM-2010. Transmittance spectra were acquired with a Shimadzu UV-3600 double-beam UV/Vis/IR spectrophotometer using standard 1cm quartz curvets. Gelation Test of 1 and 2: In a typical experiment, compound 1 or 2 (0.1 5 wt%) was dissolved in 1.0 nitric acid (100 µl) or sodium hydroxide solution by heating. The mixture was left to cool to room temperature. When the mixture appeared as a solid-like material, the container was inverted. The sample was considered to be a gel if it did not deform. ph Dependence of Fluorescence Hydrogel: To diluted nitric acid and sodium hydroxide solutions (50 ml) of different molar concentrations, compound 1 (3 mg) was dissolved, and the ph of the mixture was measured. The excitation and emission spectra were corrected for the wavelength-dependent lamp intensity and detector response, respectively. The pulsed excitation source was generated using the 330 nm of the Xenon lamp for 1. Crystallographic Structure Determinations: Crystal data for 1 and 2 were collected on a Bruker Smart diffractometer equipped with a graphite monochromated Mo K ( = 0.71073) radiation source and a CCD detector. The 45 frames of two dimensional diffraction images were collected and processed to obtain the cell parameters and orientation matrix. The first 50 frames were retaken after complete data collection. The crystal showed no significant decay. The frame data were processed to give structure factors using the SAIT. S1 Crystal data for 1 2HO 3 were collected at 100K with synchrotron radiation ( = 0.82657) on a 6BX Bruker Proteum 300 CCD detector with a platinum coated double crystal monochromator at the S2
Pohang Accelerator Laboratory, Korea. The Proteum 2 (Ver. 1.0.22) S2 was used for data collection, cell refinement, and reduction. All structure were solved by direct methods and refined by full matrix least squares methods on F 2 for all data using SHELXTL software. S3 The non-hydrogen atoms were refined anisotropically. The hydrogen atoms were placed in calculated positions and refined with a riding model with U iso constrained to be 1.2 times U eq of the parent atom. In the absence of significant anomalous scattering effects, no absolute configuration could determine for 1. Preparation of Single Crystal: 1 and 2 were prepared by evaporation from methanol or water solution containing equimolar amounts of hydrogen acceptor and donor moieties followed by drying in vacuo. For example, the 2/HO 3 1/2 salt was prepared by the mixture of 2 (0.016 g, 0.05 mmol) in methanol (2 ml), followed by drying in vacuo after it was concentrated methanol. S3
Scheme S1. Synthetic method of 1. O OH i. SOCl 2, triethyl amine ii. triethyl amine, 2,6-diaminopyridine i ii O H 1 H O,'-Bis(4-pyridylcarbonyl)-2,6-diaminopyridine (1) S4. Thionyl chloride (11.89 g, 100 mmol) was added dropwise to isonicotinic acid (12.31 g, 100 mmol) and triethylamine (10.11 g, 100 mmol) in chloroform. The mixture was refluxed for 2 h and cooled down to room temperature. Then an acetonitrile solution of diaminopyridine (5.45 g, 50 mmol and triethylamine (10.11 g, 100 mmol) were added dropwise to the resulting isonicotinyl chloride solution, cooled by salt and ice water. The solution was stirred for 12 h, and then water was added. From the resulting solution, yellow powder was filtered and washed with a dilute a 2 CO 3 solution, distilled water, and then a small amount of cold methanol. The product L was obtained as yellowish white powder (8.88 g, 55.8%). 1 H MR (300 MHz, DMSO-d 6 ): 10.93 (s, 2H HCO), 8.78 (dd, 4H CH), 7.89 (dd, 4H CCH), 7.9 (m, 3H CHCHCHC). 13 C MR (75.4 MHz, DMSO-d 6 ): 165.5, 150.8, 150.3, 141.5 122.3 112.5. HRMS (m/z) Calcd. for C 17 H 13 5 O 2 : 319.1069. Found: 319.1086 (M + ). Scheme S Synthetic method of 1. O i ii H OH O i. SOCl 2, triethyl amine ii. triethyl amine, 1,3-diaminobenzene 2 O H,'-(1,3-phenylene)diisonicotinamide (2) S5. Thionyl chloride (1.19 g, 10.0 mmol) was added dropwise to isonicotinic acid (1.23 g, 10.0 mmol) and triethylamine (1.01 g, 10.0 S4
mmol) in chloroform. The mixture was refluxed for 2 h and cooled down to room temperature. Then an acetonitrile solution of 1,3-phenylenediamine (0.540 g, 5.00 mmol and triethylamine (1.01 g, 10.0 mmol) were added dropwise to the resulting isonicotinyl chloride solution, cooled by salt and ice water. The solution was stirred for 12 h, and then water was added. From the resulting solution, yellow powder was filtered and washed with a dilute a 2 CO 3 solution, distilled water, and then a small amount of cold methanol. The product L was obtained as yellowish white powder (1.50 g, 94.3%). S5
-1.5-2.0 Hwat Flow / mw -2.5-3.0-3.5 (b) (a) -4.0-4.5 30 40 50 60 70 80 90 Temperature / o C Figure S1. Differential scanning calorimetry curves of hydrogel 1 obtained at (a) ph 7 and (b) ph 13. S6
Intensity / a.u. 240 200 160 120 80 ph 1 ph 2 ph 3 ph 4 ph 5 ph 7 ph 10 ph 11 ph 13 solution 40 0 350 400 450 500 550 600 wavelength / nm Figure S2. Fluorescence spectra of the hydrogel 1 (0.1 wt%) prepared at different ph values. S7
Table S1. Crystal and experimental data. 1 (ph 7) 1 2HO 3 2 Formula C 17 H 13 5 O 2 C 18 H 14 4 O 2 C 18 H 18 7 O 9 Formula weight 319.32 318.33 476.39 Temperature (K) 173(2) 173(2) 100 Crystal system Orthorhombic Triclinic Ticlinic Space group P2 1 2 1 2 1 P-1 P-1 Z 4 2 2 a (Å) 17.1841(9) 7.6293(9) 8.9200(18) b (Å) 12.4648(7) 8.9099(11) 11.111(2) c (Å) 6.7661(4) 12.3769(15) 11.748(2) (º) 72.542(2) 110.96(3) (º) 72.226(2) 100.17(3) (º) 77.396(2) 94.53(3) V (Å 3 ) 1449.27(14) 756.81(16) 1057.4(4) D x (g/cm 3 ) 1.463 1.397 1.496 2 max (º) 56.58 56.62 48 R 0.0718 0.0728 0.1307 wr 0.1438 0.1299 0.3780 o. of reflection used [ > 2(I)] 3229 3409 2865 Diffractometer Bruker SMART CCD system Bruker SMART CCD system 6BX Bruker Proteum 300 CCD Structure determination SHELXTL SHELXTL SHELXTL Refinement full-matrix full-matrix full-matrix S8
Figure S3. Molecular structure of 1. (ph 7) Dihedral angles: A---B 29.69(9)º; B---C 45.15(9)º; A---C 45.15(9)º. Figure S4. Packing structure of 1 (ph 7) showing intermolecular hydrogen bonds (dashed lines) and - stacking interactions of 3.4 Å (dashed arrows). S9
Figure S5. Representation of intermolecular hydrogen bonds of 1 (ph 7) (dashed lines) [symmetry operations: (A) -x, y - 1/2, -z + 3/2; (B) -x, y + 1/2, -z + 3/2; (c) x, y + 1, z]. Table S2. Intermolecular hydrogen bonds geometry (Å, º) for 1 D-H A D-H H A D A D-H A 4-H 1B 0.88 2.289 3.152(4) 166.76 C14-H 1B 0.95 2.600 3.281(4) 128.89 C15-H O1B 0.95 2.528 3.247(4) 132.61 Symmetry operation used to generate equivalent atoms: (B) -x, y + 1/2, -z + 3/2. S10
Figure S6. Molecular structure of 1 2HO 3. Dihedral angles: A---B 21.61(26) ; B---C 1.95(34) ; A---C 22.38(27). Figure S7. Representation of intermolecular hydrogen bonds of 1 2HO 3 (dashed lines) [Symmetry operations: (A) x 1, y, z 1; (B) x, -y + 1, -z + 2; (C) x + 2, -y + 1, -z + 3; (D) x + 1, y, z + 1; (E) x + 1, y, z; (E) x + 1, y, z; (F) x, -y + 2, -z + 1; (G) x 1, y, z; (H) x + 1, -y + 1, -z + 2; (I) x + 3, -y + 1, -z + 3; (J) x + 2, -y + 2, -z + 2; (K) x + 2, -y + 1, -z + 3]. S11
Table S3. Intermolecular hydrogen bonds geometry (Å, ) for 1 (ph 2). D-H A D-H H A D A D-H A 1-H O5C 0.86 1.945 2.801(4) 173.27 4-H O8G 0.86 2.361 3.207(6) 167.95 5-H O4B 0.86 1.889 2.744(4) 173.20 C2-H O7D 0.93 2.543 3.207(7) 128.65 C3-H O4 0.93 2.449 3.264(5) 146.30 C14-H O8G 0.93 2.277 3.205(6) 175.86 C15-H O9H 0.93 2.439 3.091(6) 127.14 C16-H O3B 0.93 2.574 3.163(5) 121.63 Symmetry operation used to generate equivalent atoms: (B) x, -y + 1, -z + 2; (C) x + 2, -y + 1, -z + 3 ; (D) x + 1, y, z + 1; (G) x 1, y, z; (H) x + 1, -y + 1, -z + 2. S12
Figure S8. Molecular structure of 2. Dihedral angles: A---B 65.76(1) º; B---C 63.49(9) º; A-- -C 14.22(13)º. S13
A layer B layer Figure S9. Packing structure of 2 showing intermolecular hydrogen bonds (dashed lines) and - stacking interactions of 3.6 3.9 Å (dashed arrows). S14
Figure S10. Representation of intermolecular hydrogen bonds (dashed lines) and - stacking interactions (dashed arrows) of 2 [symmetry operations: (A) x, y, z + 1; (B) -x + 1, -y + 1, -z + 2; (C) x + 1, y, z 1]. Table S4. Intermolecular hydrogen bonds geometry (Å, º) for 2 D-H A D-H H A D A D-H A 3A-H 1 0.88 2.109 2.948(3) 159.07 C4-H O1B 0.95 2.375 3.310(4) 168.09 2C-H 4 0.88 2.093 2.966(3) 171.38 Symmetry operation used to generate equivalent atoms: (A) x, y, z + 1; (B) -x + 1, -y + 1, -z + 2; (C) x + 1, y, z 1. S15
References S1. Atkinson, I. M.; Lindoy, L. F.; Matthews, O. A.; Meehan, G. V.; Sobolev, A..; White, A. H. Aust. J. Chem. 1994, 47, 1155. S2. Bruker, SMART and SAIT: Area Detector Control and Integration Software Ver. 5.0; Bruker Analytical X-ray Instruments: Madison, Wisconsin, 1998. S3. Bruker, SHELXTL: Structure Determination Programs Ver. 5.16; Bruker Analytical X- ray Instruments: Madison, Wisconsin, 1998. S4. Shin, Y. W.; Kim, T. H.; Lee, K. Y.; Park, K. M.; Han, S. W.; Lee, S. S.; Kim, J. S.; Kim, J. Bull. Korean Chem. Soc. 2005, 26, 473-476. S5. Kouketsu, T.; Kakimoto, M.; Jikei, M.; Kim, S. Y. Polymer J. 2004, 36, 513-518. S16