S1 Chemistry at Boron: Synthesis and Properties of Red to Near-IR Fluorescent Dyes based on Boron Substituted Diisoindolomethene Frameworks Gilles Ulrich, a, * Sebastien Goeb a, Antoinette De Nicola a, Pascal Retailleau b and Raymond Ziessel a* Supporting Information (75 pages) Table of Contents Pages 1) General Methods S2 2) X-ray crystal structure determination parameters of compound 6c, 8, 11, 13-16 S3 3) Packing of compounds 13, 14, 11 and 15, Figures S1 to S4 S4-S5 4) NMR traces for all compounds Figures S4 to S62 S6 5) Absorption and emission spectrum for 6a-c, 7-16, 20a-b, 21c, 23a Figures S63 to S82 S67 3) References S75
S2 1) General Methods. The 300 and 400 ( 1 H), 75.47 ( 13 C) MHz NMR spectra were recorded at room temperature with perdeuterated solvents with residual protiated solvent signals providing internal references. The 128.4 ( 11 B) MHz NMR spectra were recorded at room temperature with B in borosilicate glass as reference. A fast-atom bombardment ZAB-HF-VB-analytical apparatus in positive mode was used with a m-nitrobenzyl alcohol (m-nba) as matrix. FT-IR spectra were recorded using a spectrometer equipped with an ATR diamond apparatus. Chromatographic purification was conducted using 40-63 µm silica gel or aluminium oxide 90 standardized. Thin layer chromatography (TLC) was performed on silica gel or aluminium oxide plates coated with fluorescent indicator. All mixtures of solvents are given in v/v ratio. The experimental procedures for each reaction were tested several times to optimally find the best conditions. UV-vis spectra were recorded using a dual-beam grating spectrophotometer with a 1 cm quartz cell. All fluorescence spectra were corrected. The fluorescence quantum yield (Φ exp ) was calculated from eq (1). F { 1 exp( A ln10) } 2 ref Φ exp = Φ (1) ref F { 1 exp( ln10) } 2 ref A nref n Here, F denotes the integral of the corrected fluorescence spectrum, A is the absorbance at the excitation wavelength, and n is the refractive index of the medium. The reference system used were rhodamine 6G in methanol (Φ ref = 0.78, λ exc = 488 nm) and cresyl violet in ethanol (Φ ref = 0.50, λ exc = 546 nm) 1 in air equilibrated water and deaerated solutions. Luminescence lifetimes were measured on a spectrofluorimeter, using software with Time-Correlated Single Photon Mode coupled to a Stroboscopic system. The excitation source was a laser diode (λ 310 nm). No filter was used for the excitation. The instrument response function was determined by using a light-scattering solution (LUDOX). Materials. THF was dried over Na-benzophenone prior to distillation. All anhydrous reactions were carried out under dry argon by using Schlenk tube techniques. 2) X-Ray diffraction data. Reflection data were collected on a Nonius-Bruker Kappa CCD diffractometer with graphitemonochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Absorption correction = Multi-scan method 2, D = 1.366 Mg/m 3, 48751 collected reflections up to θ max = 23.3, 7675 unique
S3 (R int = 0.023), structure solution 3 : direct methods, model refinement: on F 2 by full matrix leastsquares methods with anisotropic thermal parameters for all non-hydrogen atoms; All hydrogen atoms were located on difference Fourier syntheses but were refined with a riding model and with U iso (H)= 1.2 Ueq (C) (1.5 for a methyl group). Structural data have been deposited with the Cambridge Crystallographic Data Centre (CIF file) as supplementary publication number see Table S1. Copies of the data can be obtained free of charge, on application to CCDC, 12 Union Road, Cambridge CB21, EZ, UK [fax: +44-1-223-336-033 or e-mail: deposit@ccdc.cam.ac.uk] TABLE S1. Crystallographic Parameters for the Structure Determination and Refinement Identification code Compound 6c Compound 8 Compound 11 Compound 13 Compound 14 Compound 15 Compound 16 CCDC code WIGQIN 746333 746334 WIGQAF 746335 746336 WIGQEJ Empirical formula C 29 H 19 B F 2 N 2 C 49 H 41 B N 2 O 2 S 2 S 2 O 2 S 2, C 69 H 45 B N 2 O 4 C 47 H 33 B N 2 C 35 H 37 B N 2 O 2 C 51 H 41 B N 2 0.5(C H 2 Cl 2 ), C H 4 O C 49 H 33 B N 2, 0.5 (C 2 H 3 N), (C 6 H 12 )] Formula weight 444.27 764.77 976.88 636.56 592.60 863.29 723.19 Temperature (K) 293(2) Wavelength (Å) 0.71073 Crystal system, Triclinic, Triclinic, Triclinic, Triclinic, Monoclinic, Triclinic, Triclinic, space group P -1 P -1 P -1 P -1 P21/c P -1 P -1 a / Å 7.310(5) 12.288(1) 14.0948(10) 11.119(4) 11.602(3) 11.0225(6) 11.294(4) b / Å 11.771(5) 13.501(2) 20.3130(11) 11.674(3) 22.532(5) 12.7998(7) 13.299(3) c / Å 13.336(5) 14.949(2) 20.3589(15) 15.572(4) 13.602(4) 17.1352(10) 14.735(4) α / deg 86.844(5) 67.988(3) 63.584(4) 78.73(2) 90 111.176(3) 101.78(2). β / deg 79.135(5) 67.773(4) 79.808(3) 73.51(2) 118.34(2) 90.737(2) 110.03(2) γ /deg 89.790(5) 67.228(4) 83.418(5) 66.73(2) 90 98.606(3) 102.17(2) Volume / Å 3 1125.2(10) 2039.6(4) 5133.7(6) 1772.5(9) 3129.6(14) 2223.0(2) 1938.4(10) Z, Calc. density (Mg/m 3 ) 2, 1.311 2, 1.245 4, 1.264 2, 1.193 4, 1.258 2, 1.290 2, 1.239 Abs. coefficient (mm -1 ) 0.088 0.173 0.078 0.068 0.205 0.23 0.071 F(000) 460 804 2040 668 1256 906 762 Crystal size (mm) 0.50x0.35x0.25 0.30x0.20x0.10 0.45x0.37x0.20 0.50x0.45x0.10 0.40x0.40x0.40 0.30x0.30x0.30 0.50x0.35x0.03 θ range for data coll. ( ) 2.26 to 26.00 1.96 to 20.09 1.98 to 20.22 2.24 to 27.51 1.81 to 21.97 1.28 to 24.80 2.02 to 22.39 Limiting indices -9 h 8-14 k 14-16 l 16-11 h 11-13 k 13-14 l 14-13 h 13-19 k 19-19 l 19-14 h 13-14 k 15-18 l 20-12 h 12, -23 k 23, -14 l 14-12 h 12, -15 k 14, 0 l 20-12 h 10, -14 k 14, -15 l 15 Reflections collected / unique 24014 / 4363 [R(int)=0.020] 12015 / 3833 [R(int) = 0.025] 17639 / 9870 [R(int) = 0.036] 12226 / 8071 [R(int) = 0.024] 21635 / 3816 [R(int) = 0.021] 16350 / 7519 [R(int) = 0.027] 10488 / 4585 [R(int) = 0.035] Completeness to θ max (%) 98.8 99.4 99.7 99.0 99.9 98.3 91.5 Absorption correction Semi-empirical from equivalents Max. and min. transm. 0.98 and 0.90 0.983 and 0.910 0.98 and 0.83-0.921 and 0.848 0.933 and 0.847 - Refinement method Full-matrix least-squares on F 2 Data / restr. / param. 4363 / 0 / 308 3833 / 0 / 509 9870 / 557/1600 8067 / 0 / 453 3821 / 4 / 384 7519 / 165 / 584 4574 / 0 / 470 Goodness-of-fit on F 2 1.019 1.028 1.074 1.036 1.044 1.102 1.073 Final R indices R1 = 0.0396, R1 = 0.0438, R1 = 0.0849, R1 = 0.0571, R1 = 0.0493, R1 = 0.0763, R1 = 0.0649,
S4 [I>2σ(I)] wr2 = 0.1012 wr2 = 0.1044 wr2 = 0.2350 wr2 = 0.1438 wr2 = 0.1354 wr2 = 0.2284 wr2 = 0.1879 Final R indices R1 = 0.0571, R1 = 0.0668, R1 = 0.1245, R1 = 0.1017, R1 = 0.0648, R1 = 0.1057, R1 = 0.0911, (all data) wr2 = 0.1120 wr2 = 0.1171 wr2 = 0.2768 wr2 = 0.1672 wr2 = 0.1464 wr2 = 0.2515 wr2 = 0.2000 Extinction coeff. 0.022(3) - - - 0.0078(13) - - Largest diff. peak and 0.197 and 0.210 and 0.462 and 0.149 and 0.784 and 0.845 and 0.223 and hole (e. Å -3 ) -0.154-0.243-0.330-0.177-0.403-0.305-0.175 Figure S1. Packing of compound 13. Cyan dashed lines indicate π-π stacking interactions between diisoindolemethene platforms related by inversion. Figure S2. Packing of compound 14. Cyan dashed lines indicate π-π stacking interactions between diisoindolemethene platforms related by inversion.
S5 Figure S3. Packing of compound 15. Cyan dashed lines indicate π-π stacking interactions between diisoindolemethene platforms related by inversion.
S6 3) NMR Spectra Traces. Figure S4. 1 H NMR of 1a in CDCl 3 200MHz
Figure S5. 13 C NMR of 1a in CDCl 3 50MHz S7
Figure S6. 1 H NMR of 2a in CDCl 3 200MHz S8
Figure S7. 13 C NMR of 2a in CDCl 3 50MHz S9
Figure S8. 1 H NMR of 2b in CDCl 3 200MHz S10
Figure S9. 1 H NMR of 3a in CDCl 3 200MHz S11
Figure S10. 1 H NMR of 3a in CDCl 3 50MHz S12
Figure S11. 1 H NMR of 3b in CDCl 3 200MHz S13
S14 Figure S12. 1 H NMR of 3c in D6-DMSO 200MHz
Figure S13. 1 H NMR of 4a in CDCl 3 200MHz S15
Figure S14. 13 C NMR of 4a in CDCl 3 50MHz S16
Figure S15. 1 H NMR of 4b in CDCl 3 300MHz S17
Figure S16. 13 C NMR of 4b in CDCl 3 75MHz S18
Figure S17. 1 H NMR of 4c in CDCl 3 200MHz S19
S20 Figure S18. 1 H NMR of 5a in CCl 4 /CDCl 3 400MHz
S21 Figure S19. 13 C NMR of 5a in CCl 4 /CDCl 3 75MHz
S22 Figure S20. 1 H NMR of 5b in CCl 4 /CDCl 3 300MHz
Figure S21. 1 H NMR of 5c in CDCl 3 300MHz S23
S24 Figure S22. 1 H NMR of 6a in CDCl 3 /CCl 4 400MHz
S25 Figure S23. 13 C NMR of 6a in CDCl 3 /CCl 4 100MHz
S26 Figure S24. 1 H NMR of 6b in CDCl 3 /CCl 4 400MHz
S27 Figure S25. 1 H NMR of 6c in CDCl 3 /CCl 4 400MHz
S28 Figure S26. 13 C NMR of 6c in CDCl 3 /CCl 4 100MHz
S29 Figure S27. 1 H NMR of 7 in CDCl 3 /CCl 4 400MHz
S30 Figure S28. 13 C NMR of 7 in CDCl 3 /CCl 4 100MHz
S31 Figure S29. 1 H NMR of 8 in CDCl 3 /CCl 4 400MHz
S32 Figure S30. 13 C NMR of 8 in CDCl 3 /CCl 4 100MHz
S33 Figure S31. 1 H NMR of 9 in CDCl 3 /CCl 4 400MHz
S34 Figure S32. 13 C NMR of 9 in CDCl 3 /CCl 4 100MHz
S35 Figure S33. 1 H NMR of 10 in CDCl 3 /CCl 4 400MHz
S36 Figure S34. 13 C NMR of 10 in CDCl 3 /CCl 4 100MHz
S37 Figure S35. 1 H NMR of 11 in CDCl 3 /CCl 4 200MHz
S38 Figure S36. 13 C NMR of 11 in CDCl 3 /CCl 4 100MHz
S39 Figure S37. 1 H NMR of 12 in d6-dmso 200MHz
Figure S38. 13 C NMR of 12 in C6D6 100MHz S40
Figure S39. 1 H NMR of 13 in CDCl 3 400MHz S41
Figure S40. 13 C NMR of 13 in CDCl 3 100MHz S42
Figure S41. 1 H NMR of 14 in CDCl 3 400MHz S43
Figure S42. 13 C NMR of 14 in CDCl 3 100MHz S44
Figure S43. 1 H NMR of 15 in CDCl 3 400MHz S45
Figure S44. 13 C NMR of 15 in CDCl 3 100MHz S46
Figure S45. 1 H NMR of 16 in CDCl 3 400MHz S47
Figure S46. 13 C NMR of 16 in C6D6 100MHz S48
S49 Figure S47. 1 H NMR of 17 in CDCl 3 300MHz. 4
S50 Figure S48. 1 H NMR of 18 in CDCl 3 300MHz. 5
S51 Figure S49. 1 H NMR of 19 in CDCl 3 300MHz. 4
S52 Figure S50. 1 H NMR of 20a in CDCl 3 /CCl 4 400MHz
S53 Figure S51. 13 C NMR of 20a in CDCl 3 /CCl 4 100MHz
S54 Figure S52. 1 H NMR of 20b in CDCl 3 400MHz
S55 Figure S53. 13 C NMR of 20b in CDCl 3 100MHz
Figure S54. 1 H NMR of 20c in CDCl 3 400MHz S56
S57 Figure S55. 13 C NMR of 20c in CDCl 3 100MHz
Figure S56. 1 H NMR of 21a in CDCl 3 400MHz S58
S59 Figure S57. 13 C NMR of 21a in CDCl 3 100MHz
S60 Figure S58. 1 H NMR of 21b in CDCl 3 400MHz
S61 Figure S59. 13 C NMR of 21b in CDCl 3 100MHz
Figure S60. 1 H NMR of 21c in CDCl 3 400MHz S62
S63 Figure S61. 13 C NMR of 21c in CDCl 3 100MHz
S64 Figure S62. 1 H NMR of 22a in CDCl 3 400MHz.
S65 4) Spectroscopy: spectra traces (recorded in CH 2 Cl 2 at RT) Figure S63. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 6a. 90000 80000 70000 60000 ε (M -1.cm -1 ) 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 850 Wavelength (nm) Figure S64. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 6b. 100000 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 850 Wavelength (nm)
S66 Figure S65. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 6c. 120000 100000 ε (M -1.cm 1 ) 80000 60000 40000 20000 0 250 350 450 550 650 750 Wavelength (nm) Figure S66. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 7. 140000 120000 100000 ε (M 1.cm 1 ) 80000 60000 40000 20000 0 250 350 450 550 650 750 850 Wavelength (nm)
S67 Figure S67. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 8. ε (M -1.cm -1 ) 90000 80000 70000 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 850 Wavelength (nm) Figure S68. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 9. ε (M -1.cm -1 ) 200000 180000 160000 140000 120000 100000 80000 60000 40000 20000 0 250 350 450 550 650 750 850 Wavelength (nm)
S68 Figure S69. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 10. 120000 100000 ε (M -1.cm -1 ) 80000 60000 40000 20000 0 250 350 450 550 650 750 850 Wavelength (nm) Figure S70. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 11. 140000 120000 100000 ε (M -1.cm -1 ) 80000 60000 40000 20000 0 250 350 450 550 650 750 850 Wavelength (nm)
S69 Figure S71. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 12. 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 Wavelength (nm) Figure S72. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 13. 90000 80000 70000 60000 ε (M -1.cm -1 ) 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 Wavelength (nm)
S70 Figure S73. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 14. 100000 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 Wavelength (nm) Figure S74. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 15. 100000 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 850 Wavelength (nm)
S71 Figure S75. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 16. 100000 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 Absorption Excitation Emission 0 250 350 450 550 650 750 Wavelength (nm) Figure S76. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 20a. ε (M -1.cm -1 ) 90000 80000 70000 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 850 Wavelength (nm)
S72 Figure S77. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 20b. 100000 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 Wavelength (nm) Figure S78. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 20c. ε (M -1.cm -1 ) 90000 80000 70000 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 Wavelength (nm)
S73 Figure S79. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 21a. 80000 70000 60000 ε (M -1.cm -1 ) 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 850 Wavelength (nm) Figure S80. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 21b. 80000 70000 60000 ε (M -1.cm -1 ) 50000 40000 30000 20000 10000 0 250 350 450 550 Wavelength (nm) 650 750
S74 Figure S81. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 21c. 100000 90000 80000 70000 ε (M -1.cm -1 ) 60000 50000 40000 30000 20000 10000 0 250 350 450 550 650 750 Wavelength (nm) Figure S82. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 23a. ε (M -1.cm -1 ) 160000 140000 120000 100000 80000 60000 40000 20000 0 250 350 450 550 650 750 850 Wavelength (nm)
S75 1 Olmsted, J. J. Phys. Chem. 1979, 83, 2581. 2 Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. J. Appl. Cryst. 1999, 32, 115. 3 Sheldrick, G.M. Acta Cryst. 2008, A 64, 112. 4 Evers, M.; Christiaens, L.; Llabres, G.; Baiwir, M. Magnetic Resonance in Chemistry, 1987, 25, 1018. 5 Hiraoka, S.; Goda, M.; Shionoya, M. J. Am. Chem. Soc., 2009, 131, 4592.