Ziessel a* Supporting Information (75 pages) Table of Contents. 1) General Methods S2

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1 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, 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

2 S2 1) General Methods. The 300 and 400 ( 1 H), ( 13 C) MHz NMR spectra were recorded at room temperature with perdeuterated solvents with residual protiated solvent signals providing internal references. The ( 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 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 = Å) at room temperature. Absorption correction = Multi-scan method 2, D = Mg/m 3, collected reflections up to θ max = 23.3, 7675 unique

3 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: or 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 WIGQAF 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 Temperature (K) 293(2) Wavelength (Å) 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) (1) (10) (4) (3) (6) (4) b / Å (5) (2) (11) (3) (5) (7) (3) c / Å (5) (2) (15) (4) (4) (10) (4) α / deg (5) (3) (4) 78.73(2) (3) (2). β / deg (5) (4) (3) 73.51(2) (2) (2) (2) γ /deg (5) (4) (5) 66.73(2) (3) (2) Volume / Å (10) (4) (6) (9) (14) (2) (10) Z, Calc. density (Mg/m 3 ) 2, , , , , , , Abs. coefficient (mm -1 ) F(000) Crystal size (mm) 0.50x0.35x x0.20x x0.37x x0.45x x0.40x x0.30x x0.35x0.03 θ range for data coll. ( ) 2.26 to to to to to to to Limiting indices -9 h 8-14 k l h k l h k l h k l h 12, -23 k 23, -14 l h 12, -15 k 14, 0 l h 10, -14 k 14, -15 l 15 Reflections collected / unique / 4363 [R(int)=0.020] / 3833 [R(int) = 0.025] / 9870 [R(int) = 0.036] / 8071 [R(int) = 0.024] / 3816 [R(int) = 0.021] / 7519 [R(int) = 0.027] / 4585 [R(int) = 0.035] Completeness to θ max (%) Absorption correction Semi-empirical from equivalents Max. and min. transm and and and and and Refinement method Full-matrix least-squares on F 2 Data / restr. / param / 0 / / 0 / / 557/ / 0 / / 4 / / 165 / / 0 / 470 Goodness-of-fit on F Final R indices R1 = , R1 = , R1 = , R1 = , R1 = , R1 = , R1 = ,

4 S4 [I>2σ(I)] wr2 = wr2 = wr2 = wr2 = wr2 = wr2 = wr2 = Final R indices R1 = , R1 = , R1 = , R1 = , R1 = , R1 = , R1 = , (all data) wr2 = wr2 = wr2 = wr2 = wr2 = wr2 = wr2 = Extinction coeff (3) (13) - - Largest diff. peak and and and and and and and and hole (e. Å -3 ) 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.

5 S5 Figure S3. Packing of compound 15. Cyan dashed lines indicate π-π stacking interactions between diisoindolemethene platforms related by inversion.

6 S6 3) NMR Spectra Traces. Figure S4. 1 H NMR of 1a in CDCl 3 200MHz

7 Figure S5. 13 C NMR of 1a in CDCl 3 50MHz S7

8 Figure S6. 1 H NMR of 2a in CDCl 3 200MHz S8

9 Figure S7. 13 C NMR of 2a in CDCl 3 50MHz S9

10 Figure S8. 1 H NMR of 2b in CDCl 3 200MHz S10

11 Figure S9. 1 H NMR of 3a in CDCl 3 200MHz S11

12 Figure S10. 1 H NMR of 3a in CDCl 3 50MHz S12

13 Figure S11. 1 H NMR of 3b in CDCl 3 200MHz S13

14 S14 Figure S12. 1 H NMR of 3c in D6-DMSO 200MHz

15 Figure S13. 1 H NMR of 4a in CDCl 3 200MHz S15

16 Figure S C NMR of 4a in CDCl 3 50MHz S16

17 Figure S15. 1 H NMR of 4b in CDCl 3 300MHz S17

18 Figure S C NMR of 4b in CDCl 3 75MHz S18

19 Figure S17. 1 H NMR of 4c in CDCl 3 200MHz S19

20 S20 Figure S18. 1 H NMR of 5a in CCl 4 /CDCl 3 400MHz

21 S21 Figure S C NMR of 5a in CCl 4 /CDCl 3 75MHz

22 S22 Figure S20. 1 H NMR of 5b in CCl 4 /CDCl 3 300MHz

23 Figure S21. 1 H NMR of 5c in CDCl 3 300MHz S23

24 S24 Figure S22. 1 H NMR of 6a in CDCl 3 /CCl 4 400MHz

25 S25 Figure S C NMR of 6a in CDCl 3 /CCl 4 100MHz

26 S26 Figure S24. 1 H NMR of 6b in CDCl 3 /CCl 4 400MHz

27 S27 Figure S25. 1 H NMR of 6c in CDCl 3 /CCl 4 400MHz

28 S28 Figure S C NMR of 6c in CDCl 3 /CCl 4 100MHz

29 S29 Figure S27. 1 H NMR of 7 in CDCl 3 /CCl 4 400MHz

30 S30 Figure S C NMR of 7 in CDCl 3 /CCl 4 100MHz

31 S31 Figure S29. 1 H NMR of 8 in CDCl 3 /CCl 4 400MHz

32 S32 Figure S C NMR of 8 in CDCl 3 /CCl 4 100MHz

33 S33 Figure S31. 1 H NMR of 9 in CDCl 3 /CCl 4 400MHz

34 S34 Figure S C NMR of 9 in CDCl 3 /CCl 4 100MHz

35 S35 Figure S33. 1 H NMR of 10 in CDCl 3 /CCl 4 400MHz

36 S36 Figure S C NMR of 10 in CDCl 3 /CCl 4 100MHz

37 S37 Figure S35. 1 H NMR of 11 in CDCl 3 /CCl 4 200MHz

38 S38 Figure S C NMR of 11 in CDCl 3 /CCl 4 100MHz

39 S39 Figure S37. 1 H NMR of 12 in d6-dmso 200MHz

40 Figure S C NMR of 12 in C6D6 100MHz S40

41 Figure S39. 1 H NMR of 13 in CDCl 3 400MHz S41

42 Figure S C NMR of 13 in CDCl 3 100MHz S42

43 Figure S41. 1 H NMR of 14 in CDCl 3 400MHz S43

44 Figure S C NMR of 14 in CDCl 3 100MHz S44

45 Figure S43. 1 H NMR of 15 in CDCl 3 400MHz S45

46 Figure S C NMR of 15 in CDCl 3 100MHz S46

47 Figure S45. 1 H NMR of 16 in CDCl 3 400MHz S47

48 Figure S C NMR of 16 in C6D6 100MHz S48

49 S49 Figure S47. 1 H NMR of 17 in CDCl 3 300MHz. 4

50 S50 Figure S48. 1 H NMR of 18 in CDCl 3 300MHz. 5

51 S51 Figure S49. 1 H NMR of 19 in CDCl 3 300MHz. 4

52 S52 Figure S50. 1 H NMR of 20a in CDCl 3 /CCl 4 400MHz

53 S53 Figure S C NMR of 20a in CDCl 3 /CCl 4 100MHz

54 S54 Figure S52. 1 H NMR of 20b in CDCl 3 400MHz

55 S55 Figure S C NMR of 20b in CDCl 3 100MHz

56 Figure S54. 1 H NMR of 20c in CDCl 3 400MHz S56

57 S57 Figure S C NMR of 20c in CDCl 3 100MHz

58 Figure S56. 1 H NMR of 21a in CDCl 3 400MHz S58

59 S59 Figure S C NMR of 21a in CDCl 3 100MHz

60 S60 Figure S58. 1 H NMR of 21b in CDCl 3 400MHz

61 S61 Figure S C NMR of 21b in CDCl 3 100MHz

62 Figure S60. 1 H NMR of 21c in CDCl 3 400MHz S62

63 S63 Figure S C NMR of 21c in CDCl 3 100MHz

64 S64 Figure S62. 1 H NMR of 22a in CDCl 3 400MHz.

65 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 ε (M -1.cm -1 ) Wavelength (nm) Figure S64. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 6b ε (M -1.cm -1 ) Wavelength (nm)

66 S66 Figure S65. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 6c ε (M -1.cm 1 ) Wavelength (nm) Figure S66. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M 1.cm 1 ) Wavelength (nm)

67 S67 Figure S67. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 8. ε (M -1.cm -1 ) Wavelength (nm) Figure S68. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 9. ε (M -1.cm -1 ) Wavelength (nm)

68 S68 Figure S69. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Wavelength (nm) Figure S70. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Wavelength (nm)

69 S69 Figure S71. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Wavelength (nm) Figure S72. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Wavelength (nm)

70 S70 Figure S73. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Wavelength (nm) Figure S74. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Wavelength (nm)

71 S71 Figure S75. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound ε (M -1.cm -1 ) Absorption Excitation Emission Wavelength (nm) Figure S76. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 20a. ε (M -1.cm -1 ) Wavelength (nm)

72 S72 Figure S77. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 20b ε (M -1.cm -1 ) Wavelength (nm) Figure S78. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 20c. ε (M -1.cm -1 ) Wavelength (nm)

73 S73 Figure S79. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 21a ε (M -1.cm -1 ) Wavelength (nm) Figure S80. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 21b ε (M -1.cm -1 ) Wavelength (nm)

74 S74 Figure S81. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 21c ε (M -1.cm -1 ) Wavelength (nm) Figure S82. Absorption (blue line), emission (green line), and excitation (red line) spectra of compound 23a. ε (M -1.cm -1 ) Wavelength (nm)

75 S75 1 Olmsted, J. J. Phys. Chem. 1979, 83, 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, Sheldrick, G.M. Acta Cryst. 2008, A 64, Evers, M.; Christiaens, L.; Llabres, G.; Baiwir, M. Magnetic Resonance in Chemistry, 1987, 25, Hiraoka, S.; Goda, M.; Shionoya, M. J. Am. Chem. Soc., 2009, 131, 4592.