Supporting Information
On the Photophysical Properties of New Luminol Derivatives and their Synthetic Phthalimide Precursors
Raúl Pérez-Ruiz,a Robert Fichtler,a Yrene Díaz,a Helfried Neumann,b Matthias Beller,b Matthieu Nicoul,c Dominik Schaniel,c Axel G. Griesbeck,*,a Axel Jacobi von Wangelin*,a.
a Department of Chemistry, University of Cologne, Germany, Greinsstrasse, 4, 50939, Köln; Fax: +49 (0) 2214705057
E-mail: ,
b Department of Physics I, University of Cologne, Germany.
c Leibniz-Institute of Catalysis, University of Rostock, Germany.
S1: This page.
S2: Absorption spectra of 17-24 in DMSO. Concentration was 2.5·10-6 M in all cases.
S3: Normalised absorption, excitation and emission spectra of 17-24.
S4: Absorption spectra of 17-24 in buffer solutions at different pH. Concentration was 1.3·10-3 M in all cases.
S5: Emission spectra of 17-24 in buffer solutions at A) pH = 3; B) pH = 7. Concentration was 2.6·10-6 M in all cases.
S6: Detailed theoretical data for compound 18: (a) vacuum, protonated (spectrum envelope peak half-width at half height 0.18 eV)
S7: Detailed theoretical data for compound 18: (b) vacuum, non-protonated (spectrum envelope peak half-width at half height 0.18 eV)
S8: Detailed theoretical data for compound 18: (c) in DMSO, protonated (spectrum envelope peak half-width at half height 0.18 eV)
S9: Detailed theoretical data for compound 18: (d) in DMSO, non-protonated (spectrum envelope peak half-width at half height 0.18 eV)
Detailed theoretical data for compound 18:
(a) vacuum, protonated (spectrum envelope peak half-width at half height 0.18 eV)
Method: RB3LYP/6-311++G(d,p) E(RB+HF-LYP) = -702.967066970 a.u.
Zero-point correction= 0.216770 (Hartree/Particle)
Thermal correction to Energy= 0.230322
Sum of electronic and zero-point Energies= -702.750297
Sum of electronic and thermal Energies= -702.736745
Number of imaginary frequencies = 0
Excited State 1: Singlet-A 3.9384 eV 314.81 nm f=0.0421
Excited State 2: Singlet-A 4.1572 eV 298.24 nm f=0.0065
Excited State 3: Singlet-A 4.3636 eV 284.13 nm f=0.0185
Excited State 4: Singlet-A 4.5815 eV 270.62 nm f=0.0159
Excited State 5: Singlet-A 4.6921 eV 264.24 nm f=0.0242
Excited State 6: Singlet-A 5.0566 eV 245.19 nm f=0.0240
Excited State 7: Singlet-A 5.1273 eV 241.81 nm f=0.0000
Excited State 8: Singlet-A 5.4702 eV 226.65 nm f=0.0004
Excited State 9: Singlet-A 5.6031 eV 221.28 nm f=0.2743
Excited State 10: Singlet-A 5.8040 eV 213.62 nm f=0.5247
(b) vacuum, non-protonated (spectrum envelope peak half-width at half height 0.18 eV)
Method: RB3LYP/6-311++G(d,p) E(RB+HF-LYP) = -702.607387683 a.u.
Zero-point correction= 0.204601 (Hartree/Particle)
Thermal correction to Energy= 0.218158
Sum of electronic and zero-point Energies= -702.402787
Sum of electronic and thermal Energies= -702.389230
Number of imaginary frequencies = 0
Excited State 1: Singlet-A 3.5272 eV 351.51 nm f=0.1489
Excited State 2: Singlet-A 4.2140 eV 294.22 nm f=0.0055
Excited State 3: Singlet-A 4.3163 eV 287.25 nm f=0.0337
Excited State 4: Singlet-A 4.4701 eV 277.36 nm f=0.0027
Excited State 5: Singlet-A 4.6968 eV 263.98 nm f=0.0008
Excited State 6: Singlet-A 4.7326 eV 261.98 nm f=0.0054
Excited State 7: Singlet-A 4.9210 eV 251.95 nm f=0.0009
Excited State 8: Singlet-A 4.9744 eV 249.24 nm f=0.0062
Excited State 9: Singlet-A 5.2103 eV 237.96 nm f=0.1746
Excited State 10: Singlet-A 5.3007 eV 233.90 nm f=0.0073
(c) in DMSO, protonated (spectrum envelope peak half-width at half height 0.18 eV)
Method: RB3LYP/6-311++G(d,p) E(RB+HF-LYP) = -703.062951316 a.u.
Zero-point correction= 0.218286 (Hartree/Particle)
Thermal correction to Energy= 0.231786
Sum of electronic and zero-point Energies= -702.844666
Sum of electronic and thermal Energies= -702.831166
Number of imaginary frequencies = 0
Excited State 1: Singlet-A 4.0751 eV 304.25 nm f=0.0787
Excited State 2: Singlet-A 4.3615 eV 284.27 nm f=0.0407
Excited State 3: Singlet-A 4.5574 eV 272.05 nm f=0.0040
Excited State 4: Singlet-A 4.6501 eV 266.62 nm f=0.0340
Excited State 5: Singlet-A 5.0458 eV 245.72 nm f=0.0071
Excited State 6: Singlet-A 5.0587 eV 245.09 nm f=0.0022
Excited State 7: Singlet-A 5.0793 eV 244.10 nm f=0.0785
Excited State 8: Singlet-A 5.5277 eV 224.30 nm f=0.3901
Excited State 9: Singlet-A 5.6510 eV 219.40 nm f=0.7289
Excited State 10: Singlet-A 5.7980 eV 213.84 nm f=0.0000
(d) in DMSO, non-protonated (spectrum envelope peak half-width at half height 0.18 eV)
Method: RB3LYP/6-311++G(d,p) RB3LYP/6-311++G(d,p) E(RB+HF-LYP) = -702.627646819 a.u.
Zero-point correction= 0.204046 (Hartree/Particle)
Thermal correction to Energy= 0.217526
Sum of electronic and zero-point Energies= -702.423601
Sum of electronic and thermal Energies= -702.410121
Number of imaginary frequencies = 0
Excited State 1: Singlet-A 3.5259 eV 351.64 nm f=0.2050
Excited State 2: Singlet-A 4.2399 eV 292.42 nm f=0.0722
Excited State 3: Singlet-A 4.2848 eV 289.36 nm f=0.0072
Excited State 4: Singlet-A 4.6732 eV 265.31 nm f=0.0011
Excited State 5: Singlet-A 4.8709 eV 254.54 nm f=0.0006
Excited State 6: Singlet-A 4.9598 eV 249.98 nm f=0.0068
Excited State 7: Singlet-A 4.9823 eV 248.85 nm f=0.0017
Excited State 8: Singlet-A 5.1652 eV 240.04 nm f=0.3382
Excited State 9: Singlet-A 5.2880 eV 234.47 nm f=0.0043
Excited State 10: Singlet-A 5.4459 eV 227.66 nm f=0.0122
Raúl Pérez-Ruiz et al. J Fluorescence -9-