CS-Symmetric Triarylborane Substituted Bisthiazole for Selective Detection of F− and CN−

ions

Ramesh Maragani, T. Sheshashena Reddy, Rajneesh Misra*

Department of Chemistry, Indian Institute of Technology Indore, Indore 452017, India.

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Table of Contents:

1) Experimental procedure, Synthesis,Sheme and optimized structures-----------------------

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2) TD-DFT UV-graphs ------------------------------------------S53) UV graphs and calculations -----------------------------S7-S19

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Experimental:

General remarks

All the chemicals were purchased from commercial sources and used without further purification. Triethylamine was received from commercial source, and distilled on KOH prior to use. 1H NMR and 13C NMR spectra were performed on 400 MHz and 100 MHz Bruker Ultra shield (Avance–III) Nano Bay spectrometer. All the spectra were recorded at 298K.1H NMR data are reported as follows: s: singlet, d: doublet, t: triplet, bs: broad singlet and coupling constants, J, are given in Hz. Chemical shifts in 1H NMR and 13C NMR spectra were reported in parts per million (ppm) with TMS (0 ppm) and CDCl3 (7.27ppm ,77.00 ppm) as standards. TLC analysis was carried out using silica gel 60 F254 plates. UV–vis absorption spectra of all compounds were recorded in THF on a carry–100 Bio UV–visible Spectrophotometer. Emission spectra were taken in a fluoromax-4p fluorimeter from Horibayovin (model: FM–100). The excitation and emission slits were 2/2 nm for the emission measurements. All the measurements were done at 298K. For UV–visi and fluorescence titrations the anion (F−, Cl−, Br−, I−, NO2

− and CN−) stock solutions were prepared in THF in the order of 10−3M. The triarylborane naphthalimide 1 stock solution was prepared (C=1mM) in THF. Working solutions of 1 and anions were freshly prepared from stock solutions. The fluorescence quantum yield (Φ) was calculated using Quinine sulfate (Φ=0.54) as reference. Column chromatography was performed on Merck silica gel (230-400 mesh). The anions were used in their tetrabutylammonium salts. The relative fluorescence quantum efficiency, (Φ), is evaluated by employing Quinine sulfate as standard (Φ=0.54) following the equation 1.

¿❑std ( I unk

I st d)( A std

Aunk)(❑unk

❑std )2

.......... 1

Where Φunk, Φstd, Iunk, Istd, Astd, Aunk, ηunk and ηstd are the fluorescence quantum efficiency, the integral of the emission intensities, the absorbance at the excitation wavelength and the refractive indexes of the corresponding solvents of the unknown samples and the standard respectively.

Absorption and fluorescence titration spectra of triarylborane substituted bisthiazole 1 (2.1×10−5

M) with TBAF in THF solvent for the binding constant of the complex formed in solution has

been estimated by using the standard Benesi−Hildebrand equation 2.

1I −I o

= 1I 1−I o

+ 1(I ¿¿1−I ¿¿o) Ka[ M ] Eq .2¿¿

Where I0 is the intensity before addition of anion, I is the intensity in the presence of F−/ CN−, I1 is

intensity upon saturation with anion, and Ka is the association constant of the complex formed. The detection limit of 1 as a fluorescent sensor for the analysis of fluoride and cyanide were

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determined from the plot of fluorescence intensity as a function of the concentration of fluoride and cyanide respectively. The detection limits of fluoride and cyanide ions using 1 were determined from the following equation: DL= K SD/S, where K=3; SD is the standard deviation of the blank solution; S is the slope of the calibration curve.29-31

Synthetic procedure

Synthesis of 5,5'-Bis-{4-[bis-(2,4,6-trimethyl-phenyl)-boranyl]-phenylethynyl}-4,4'-dihexyl-[2,2']bithiazolyl 1: 5,5'-Dibromo-4,4'-dihexyl-[2,2']bithiazolyl d ( 100 mg, 0.20 mmol), (4–ethynylphenyl)dimesitylborane (156 mg, 0.44 mmol) were dissolved in dry THF (20ml), added triethylamine (5 ml), Pd(PPh3)4 (0.013 g, 0.01 mmol), stirred for 24 h at 100 oC, after completion of the reaction, the reaction mixture was concentrated under reduced pressure, the crude compound was purified by column chromatography on silica, using hexane/ DCM (75:25) to get 1 as a yellow solid (0.130 g, 62 %); 1H NMR (400 MHz, CDCl3): δ = 7.54 (m, 8H), 6.84 (s, 8H), 2.96 (t, 4H), 2.33 (s, 12H), 2.02 (s, 24H), 1.83 (t, 4H), 1.35 (m, 12H), 0.89 (t, 6H) ppm; 13C NMR (100 MHz, CDCl3): δ = 163.57, 159.10, 140.87, 139.00, 136.15, 130.81, 128.28, 125.69, 115.52, 99.32, 81.96, 31.59, 29.76, 28.91, 23.50, 22.64, 21.30, 14.18 ppm; HRMS (ESI): calcd. for C70H78N2S2B2 1055.5706 [M+] found 1055.5709.

Scheme S1. Synthesis of bisthiazole d.

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1

1F

1CN

Figure S1: Geometry optimized structures of bisthiazole triarylborane dyad 1, 1-F and 1-CN in THF solution with Gaussian 09 at the TD-

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Figure S2: The comparison of experimental and calculated (TD-DFT at B3LYP level)

absorption spectrum of bisthiazole triarylborane dyad 1, 1-F and 1-CN in THF solution.

1

HOMO LUMO

1-F

HOMO -1 LUMO +1

1CN

HOMO-1

Figure S3: The major transitions of bisthiazole triarylborane dyad 1, 1-F and 1-CN.

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1

1F

1 CN

Figure S4: The calculated TD-DFT at B3LYP level absorption spectrums of bisthiazole

triarylborane dyad 1, 1-F and 1-CN in THF solution.

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Figure S5: Effect of anions on the absorption spectrum of 1 (2.1×10−5 M) in THF solvent.

Figure S6: Effect of anions on the fluorescence spectrum of 1 ((2.1×10−5 M)) (λex 473 nm) in THF solvent.

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Figure S7: Job’s plot of 1 and TBAF, in THF solution. The absorbance was collected at 416 nm.

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Figure S8: Effect of other anions in the presence 1+ F- in THF solvent.

Figure S9: Job’s plot of 1 and TBACN, in THF solution. The absorbance was collected at 416 nm.

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Figure S10: Effect of other anions in the presence 1+ CN-

in THF solvent.

Figure S11. Benesi–Hildebrand plot of 1 by plotting 1/(I0-I) as a function of 1/[ F−] for the calculation of binding constant (K). Here I refer to the fluorescence intensity of 1 at 424 nm at a given F− concentration and Io corresponds to the initial fluorescence intensity of 1 at 424 nm in the absence of F−.

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Figure S12: Benesi–Hildebrand plot of 1 by plotting 1/(I0-I) as a function of 1/[ CN−] for the calculation of binding constant (K). Here I refer to the fluorescence intensity of 1 at 424 nm at a given CN− concentration and Io corresponds to the initial fluorescence intensity of 1 at 424 nm in the absence of CN−.

Figure S13: 1H–NMR titration spectra of bisthiazole triarylborane dyad 1 with TBACN in CDCl3

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Figure S14: The bisthiazole triarylborane dyad 1 in THF solvent under UV light in the presence of different anions.

Figure S15. 1H NMR Spectra of bisthiazole triarylborane dyad 1.

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Figure S16. 13C NMR Spectra of bisthiazole triarylborane dyad 1.

Figure S17. HRMS Spectra of bisthiazole triarylborane dyad 1.

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From the chart 1 and figure 4 it can be observed the phenyl protons (H-1) singlet signal at 6.84 ppm are shielded upon addition of fluoride anion and the new signal is observed at 6.57 ppm. The signal at 6.57 ppm corresponds to the H-1 protons. Due to the shielded nature of phenyl protons (H-1) singlet signal at 6.84 ppm, these protons intensity is decreased and new the same protons new signal appeared at 6.57 ppm.

Chart S1: The triarylborane substituted bisthiazole 1.

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IV. DFT Calculations.

IV. DFT calculation data of the ferrocenyl substituted triphenylamine donor-acceptor bisthiazole

triarylborane dyad 1, 1-F and 1-CN Calculation method: B3LYP/6-31+G** for C, H, N with

Gaussian 091.

Data for compound 1:

--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.835896 -2.109051 -0.024247 2 7 0 -1.539377 -1.051299 -0.017330 3 6 0 -0.355832 -5.781931 -0.018457 4 6 0 -0.455371 -4.567194 -0.018927 5 6 0 -0.564088 -3.170373 -0.019445 6 6 0 -1.714789 -2.396558 -0.016383 7 6 0 -0.262321 -0.738835 -0.021520 8 16 0 -0.835896 2.109051 -0.024247 9 7 0 1.539377 1.051299 -0.017330 10 6 0 0.355832 5.781931 -0.018457 11 6 0 0.455371 4.567194 -0.018927 12 6 0 0.564088 3.170373 -0.019445 13 6 0 1.714789 2.396558 -0.016383 14 6 0 0.262321 0.738835 -0.021520 15 6 0 0.229536 7.075716 -0.021363 16 6 0 1.390367 7.875466 -0.081574 17 6 0 -1.030032 7.709137 0.039622 18 6 0 1.284417 9.259626 -0.092396 19 1 0 2.362274 7.394761 -0.127446 20 6 0 -1.112962 9.095043 0.055215 21 1 0 -1.927585 7.100406 0.080812 22 6 0 0.035283 9.914606 -0.015645 23 1 0 2.188884 9.857145 -0.157440 24 1 0 -2.090413 9.564883 0.116623 25 5 0 -0.071772 11.485034 -0.011116 26 6 0 1.118836 12.327410 -0.630493 27 6 0 -1.355074 12.159150 0.626652 28 6 0 1.837411 13.265196 0.167121 29 6 0 1.539377 12.148363 -1.973109 30 6 0 -2.159190 13.058049 -0.128531 31 6 0 -1.755602 11.874422 1.958445 32 6 0 2.928707 13.950758 -0.366941 33 6 0 1.482515 13.523911 1.617156 34 6 0 2.631922 12.869441 -2.475281 35 6 0 0.802251 11.259282 -2.955660

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36 6 0 -3.309300 13.615589 0.434507 37 6 0 -1.830377 13.414685 -1.564078 38 6 0 -2.899353 12.478188 2.494985 39 6 0 -0.981168 10.939721 2.870334 40 6 0 3.345925 13.770919 -1.690913 41 1 0 3.472004 14.647182 0.268784 42 1 0 0.439281 13.828779 1.732526 43 1 0 1.626623 12.632270 2.238570 44 1 0 2.114731 14.312554 2.034228 45 1 0 2.926025 12.718873 -3.512433 46 1 0 0.124221 10.556949 -2.470774 47 1 0 0.206690 11.866939 -3.648595 48 1 0 1.504645 10.680001 -3.564180 49 6 0 -3.696598 13.346655 1.750568 50 1 0 -3.918161 14.284737 -0.170145 51 1 0 -2.582449 14.093571 -1.975278 52 1 0 -0.854557 13.901501 -1.646634 53 1 0 -1.802545 12.529831 -2.209449 54 1 0 -3.173127 12.259887 3.525492 55 1 0 -1.373025 9.917416 2.819355 56 1 0 0.080071 10.881725 2.622099 57 1 0 -1.062590 11.267415 3.911371 58 6 0 4.524345 14.537585 -2.241192 59 6 0 -4.918544 13.999718 2.350334 60 1 0 4.337212 15.617828 -2.228982 61 1 0 5.427164 14.363644 -1.644635 62 1 0 4.743184 14.248717 -3.272795 63 1 0 -4.702941 15.027393 2.668743 64 1 0 -5.738952 14.053143 1.627477 65 1 0 -5.274352 13.453156 3.228368 66 6 0 -0.229536 -7.075716 -0.021363 67 6 0 -1.390367 -7.875466 -0.081574 68 6 0 1.030032 -7.709137 0.039622 69 6 0 -1.284417 -9.259626 -0.092396 70 1 0 -2.362274 -7.394761 -0.127446 71 6 0 1.112962 -9.095043 0.055215 72 1 0 1.927585 -7.100406 0.080812 73 6 0 -0.035283 -9.914606 -0.015645 74 1 0 -2.188884 -9.857145 -0.157440 75 1 0 2.090413 -9.564883 0.116623 76 5 0 0.071772 -11.485034 -0.011116 77 6 0 -1.118836 -12.327410 -0.630493 78 6 0 1.355074 -12.159150 0.626652 79 6 0 -1.837411 -13.265196 0.167121 80 6 0 -1.539377 -12.148363 -1.973109 81 6 0 2.159190 -13.058049 -0.128531

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82 6 0 1.755602 -11.874422 1.958445 83 6 0 -2.928707 -13.950758 -0.366941 84 6 0 -1.482515 -13.523911 1.617156 85 6 0 -2.631922 -12.869441 -2.475281 86 6 0 -0.802251 -11.259282 -2.955660 87 6 0 3.309300 -13.615589 0.434507 88 6 0 1.830377 -13.414685 -1.564078 89 6 0 2.899353 -12.478188 2.494985 90 6 0 0.981168 -10.939721 2.870334 91 6 0 -3.345925 -13.770919 -1.690913 92 1 0 -3.472004 -14.647182 0.268784 93 1 0 -0.439281 -13.828779 1.732526 94 1 0 -1.626623 -12.632270 2.238570 95 1 0 -2.114731 -14.312554 2.034228 96 1 0 -2.926025 -12.718873 -3.512433 97 1 0 -0.124221 -10.556949 -2.470774 98 1 0 -0.206690 -11.866939 -3.648595 99 1 0 -1.504645 -10.680001 -3.564180 100 6 0 3.696598 -13.346655 1.750568 101 1 0 3.918161 -14.284737 -0.170145 102 1 0 2.582449 -14.093571 -1.975278 103 1 0 0.854557 -13.901501 -1.646634 104 1 0 1.802545 -12.529831 -2.209449 105 1 0 3.173127 -12.259887 3.525492 106 1 0 1.373025 -9.917416 2.819355 107 1 0 -0.080071 -10.881725 2.622099 108 1 0 1.062590 -11.267415 3.911371 109 6 0 -4.524345 -14.537585 -2.241192 110 6 0 4.918544 -13.999718 2.350334 111 1 0 -4.337212 -15.617828 -2.228982 112 1 0 -5.427164 -14.363644 -1.644635 113 1 0 -4.743184 -14.248717 -3.272795 114 1 0 4.702941 -15.027393 2.668743 115 1 0 5.738952 -14.053143 1.627477 116 1 0 5.274352 -13.453156 3.228368 117 6 0 -3.118060 -3.030917 -0.012133 118 6 0 3.118060 3.030917 -0.012133 119 1 0 -3.115539 -3.898156 0.614596 120 1 0 3.115539 3.898156 0.614596 121 1 0 -3.828324 -2.323095 0.361248 122 1 0 3.828324 2.323095 0.361248 123 1 0 3.713021 2.585818 -0.782073 124 1 0 -3.713021 -2.585818 -0.782073 ---------------------------------------------------------------------

Total Energy, E(TD-HF/TD-KS) = -3276.00290938

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Data for compound 1F:

--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.838716 -2.107931 0.071816 2 7 0 1.537969 -1.053356 0.064899 3 6 0 0.348100 -5.782402 0.066026 4 6 0 0.449262 -4.567799 0.066496 5 6 0 0.559848 -3.171125 0.067014 6 6 0 1.711582 -2.398849 0.063952 7 6 0 0.261333 -0.739185 0.069089 8 16 0 0.838716 2.107931 0.071816 9 7 0 -1.537969 1.053356 0.064899 10 6 0 -0.348100 5.782402 0.066026 11 6 0 -0.449262 4.567799 0.066496 12 6 0 -0.559848 3.171125 0.067014 13 6 0 -1.711582 2.398849 0.063952 14 6 0 -0.261333 0.739185 0.069089 15 6 0 -0.220074 7.076016 0.068932 16 6 0 -1.379834 7.877318 0.129143 17 6 0 1.040340 7.707753 0.007947 18 6 0 -1.272033 9.261335 0.139965 19 1 0 -2.352382 7.397914 0.175015 20 6 0 1.125124 9.093546 -0.007646 21 1 0 1.937078 7.097822 -0.033243 22 6 0 -0.022024 9.914644 0.063214 23 1 0 -2.175700 9.860064 0.205009 24 1 0 2.103203 9.562078 -0.069054 25 5 0 0.087131 11.484928 0.058685 26 6 0 -1.102349 12.328895 0.678062 27 6 0 1.371334 12.157327 -0.579083 28 6 0 -1.819670 13.267641 -0.119552 29 6 0 -1.523129 12.150410 2.020678 30 6 0 2.176651 13.055150 0.176100 31 6 0 1.771480 11.872064 -1.910876 32 6 0 -2.910048 13.954662 0.414510 33 6 0 -1.464428 13.525882 -1.569587 34 6 0 -2.614710 12.872950 2.522850 35 6 0 -0.787193 11.260345 3.003229 36 6 0 3.327506 13.611151 -0.386938 37 6 0 1.848315 13.412225 1.611647 38 6 0 2.916038 12.474299 -2.447416 39 6 0 0.995797 10.938399 -2.822765 40 6 0 -3.327506 13.775381 1.738482 41 1 0 -3.452413 14.651812 -0.221215

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42 1 0 -0.420788 13.829354 -1.684957 43 1 0 -1.609728 12.634434 -2.191001 44 1 0 -2.095589 14.315369 -1.986659 45 1 0 -2.909013 12.722774 3.560002 46 1 0 -0.110103 10.557106 2.518343 47 1 0 -0.190820 11.867205 3.696164 48 1 0 -1.490362 10.682004 3.611749 49 6 0 3.714444 13.341699 -1.702999 50 1 0 3.937260 14.279484 0.217714 51 1 0 2.601294 14.090105 2.022847 52 1 0 0.873147 13.900346 1.694203 53 1 0 1.819299 12.527409 2.257018 54 1 0 3.189519 12.255632 -3.477923 55 1 0 1.386286 9.915570 -2.771786 56 1 0 -0.065519 10.881822 -2.574530 57 1 0 1.077657 11.265984 -3.863802 58 6 0 -4.504900 14.543622 2.288761 59 6 0 4.937262 13.993128 -2.302765 60 1 0 -4.316322 15.623614 2.276551 61 1 0 -5.407951 14.370889 1.692204 62 1 0 -4.724125 14.255047 3.320364 63 1 0 4.723033 15.021090 -2.621174 64 1 0 5.757741 14.045455 -1.579908 65 1 0 5.292338 13.446091 -3.180799 66 6 0 0.220074 -7.076016 0.068932 67 6 0 1.379834 -7.877318 0.129143 68 6 0 -1.040340 -7.707753 0.007947 69 6 0 1.272033 -9.261335 0.139965 70 1 0 2.352382 -7.397914 0.175015 71 6 0 -1.125124 -9.093546 -0.007646 72 1 0 -1.937078 -7.097822 -0.033243 73 6 0 0.022024 -9.914644 0.063214 74 1 0 2.175700 -9.860064 0.205009 75 1 0 -2.103203 -9.562078 -0.069054 76 5 0 -0.087131 -11.484928 0.058685 77 6 0 1.102349 -12.328895 0.678062 78 6 0 -1.371334 -12.157327 -0.579083 79 6 0 1.819670 -13.267641 -0.119552 80 6 0 1.523129 -12.150410 2.020678 81 6 0 -2.176651 -13.055150 0.176100 82 6 0 -1.771480 -11.872064 -1.910876 83 6 0 2.910048 -13.954662 0.414510 84 6 0 1.464428 -13.525882 -1.569587 85 6 0 2.614710 -12.872950 2.522850 86 6 0 0.787193 -11.260345 3.003229 87 6 0 -3.327506 -13.611151 -0.386938

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88 6 0 -1.848315 -13.412225 1.611647 89 6 0 -2.916038 -12.474299 -2.447416 90 6 0 -0.995797 -10.938399 -2.822765 91 6 0 3.327506 -13.775381 1.738482 92 1 0 3.452413 -14.651812 -0.221215 93 1 0 0.420788 -13.829354 -1.684957 94 1 0 1.609728 -12.634434 -2.191001 95 1 0 2.095589 -14.315369 -1.986659 96 1 0 2.909013 -12.722774 3.560002 97 1 0 0.110103 -10.557106 2.518343 98 1 0 0.190820 -11.867205 3.696164 99 1 0 1.490362 -10.682004 3.611749 100 6 0 -3.714444 -13.341699 -1.702999 101 1 0 -3.937260 -14.279484 0.217714 102 1 0 -2.601294 -14.090105 2.022847 103 1 0 -0.873147 -13.900346 1.694203 104 1 0 -1.819299 -12.527409 2.257018 105 1 0 -3.189519 -12.255632 -3.477923 106 1 0 -1.386286 -9.915570 -2.771786 107 1 0 0.065519 -10.881822 -2.574530 108 1 0 -1.077657 -11.265984 -3.863802 109 6 0 4.504900 -14.543622 2.288761 110 6 0 -4.937262 -13.993128 -2.302765 111 1 0 4.316322 -15.623614 2.276551 112 1 0 5.407951 -14.370889 1.692204 113 1 0 4.724125 -14.255047 3.320364 114 1 0 -4.723033 -15.021090 -2.621174 115 1 0 -5.757741 -14.045455 -1.579908 116 1 0 -5.292338 -13.446091 -3.180799 117 6 0 3.114004 -3.035084 0.059702 118 6 0 -3.114004 3.035084 0.059702 119 1 0 3.110323 -3.902319 -0.567027 120 1 0 -3.110323 3.902319 -0.567027 121 1 0 3.825214 -2.328212 -0.313679 122 1 0 -3.825214 2.328212 -0.313679 123 1 0 -3.709560 2.590781 0.829642 124 1 0 3.709560 -2.590781 0.829642 125 9 0 0.575200 -11.535936 -1.252656 126 9 0 -0.575200 11.535936 -1.252656 ---------------------------------------------------------------------

Total Energy, E(TD-HF/TD-KS) = -3475.46227759

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Data for compound 1CN:

--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.845235 -2.105325 0.122617 2 7 0 1.534702 -1.058111 0.115700 3 6 0 0.330203 -5.783451 0.116827 4 6 0 0.435124 -4.569167 0.117297 5 6 0 0.550031 -3.172842 0.117815 6 6 0 1.704150 -2.404134 0.114753 7 6 0 0.259044 -0.739990 0.119890 8 16 0 0.845235 2.105325 0.122617 9 7 0 -1.534702 1.058111 0.115700 10 6 0 -0.330203 5.783451 0.116827 11 6 0 -0.435124 4.569167 0.117297 12 6 0 -0.550031 3.172842 0.117815 13 6 0 -1.704150 2.404134 0.114753 14 6 0 -0.259044 0.739990 0.119890 15 6 0 -0.198174 7.076663 0.119733 16 6 0 -1.355449 7.881550 0.179944 17 6 0 1.064189 7.704496 0.058748 18 6 0 -1.243365 9.265227 0.190766 19 1 0 -2.329476 7.405158 0.225816 20 6 0 1.153261 9.090020 0.043155 21 1 0 1.959035 7.091793 0.017558 22 6 0 0.008660 9.914664 0.114015 23 1 0 -2.145175 9.866749 0.255810 24 1 0 2.132785 9.555523 -0.018253 25 5 0 0.122674 11.484602 0.109486 26 6 0 -1.064189 12.332247 0.728863 27 6 0 1.408951 12.153024 -0.528282 28 6 0 -1.778601 13.273208 -0.068751 29 6 0 -1.485519 12.155065 2.071479 30 6 0 2.217043 13.048350 0.226901 31 6 0 1.808213 11.866524 -1.860075 32 6 0 -2.866847 13.963600 0.465311 33 6 0 -1.422561 13.530348 -1.518786 34 6 0 -2.574858 12.880979 2.573651 35 6 0 -0.752341 11.262726 3.054030 36 6 0 3.369613 13.600787 -0.336137 37 6 0 1.889814 13.406440 1.662448 38 6 0 2.954629 12.465214 -2.396615 39 6 0 1.029644 10.935264 -2.771964 40 6 0 -3.284858 13.785612 1.789283 41 1 0 -3.407052 14.662425 -0.170414

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42 1 0 -0.377987 13.830589 -1.634156 43 1 0 -1.570620 12.639354 -2.140200 44 1 0 -2.051276 14.321785 -1.935858 45 1 0 -2.869625 12.731715 3.610803 46 1 0 -0.077431 10.557395 2.569144 47 1 0 -0.154093 11.867738 3.746965 48 1 0 -1.457296 10.686564 3.662550 49 6 0 3.755715 13.330139 -1.652198 50 1 0 3.981433 14.267230 0.268515 51 1 0 2.644887 14.081986 2.073648 52 1 0 0.916161 13.897576 1.745004 53 1 0 1.858060 12.521718 2.307819 54 1 0 3.227432 12.245702 -3.427122 55 1 0 1.416966 9.911232 -2.720985 56 1 0 -0.031842 10.881972 -2.523729 57 1 0 1.112517 11.262594 -3.813001 58 6 0 -4.459869 14.557493 2.339562 59 6 0 4.980543 13.977780 -2.251964 60 1 0 -4.267950 15.636896 2.327352 61 1 0 -5.363450 14.387555 1.743005 62 1 0 -4.679986 14.269598 3.371165 63 1 0 4.769497 15.006400 -2.570373 64 1 0 5.801180 14.027568 -1.529107 65 1 0 5.333925 13.429647 -3.129998 66 6 0 0.198174 -7.076663 0.119733 67 6 0 1.355449 -7.881550 0.179944 68 6 0 -1.064189 -7.704496 0.058748 69 6 0 1.243365 -9.265227 0.190766 70 1 0 2.329476 -7.405158 0.225816 71 6 0 -1.153261 -9.090020 0.043155 72 1 0 -1.959035 -7.091793 0.017558 73 6 0 -0.008660 -9.914664 0.114015 74 1 0 2.145175 -9.866749 0.255810 75 1 0 -2.132785 -9.555523 -0.018253 76 5 0 -0.122674 -11.484602 0.109486 77 6 0 1.064189 -12.332247 0.728863 78 6 0 -1.408951 -12.153024 -0.528282 79 6 0 1.778601 -13.273208 -0.068751 80 6 0 1.485519 -12.155065 2.071479 81 6 0 -2.217043 -13.048350 0.226901 82 6 0 -1.808213 -11.866524 -1.860075 83 6 0 2.866847 -13.963600 0.465311 84 6 0 1.422561 -13.530348 -1.518786 85 6 0 2.574858 -12.880979 2.573651 86 6 0 0.752341 -11.262726 3.054030 87 6 0 -3.369613 -13.600787 -0.336137

S23

88 6 0 -1.889814 -13.406440 1.662448 89 6 0 -2.954629 -12.465214 -2.396615 90 6 0 -1.029644 -10.935264 -2.771964 91 6 0 3.284858 -13.785612 1.789283 92 1 0 3.407052 -14.662425 -0.170414 93 1 0 0.377987 -13.830589 -1.634156 94 1 0 1.570620 -12.639354 -2.140200 95 1 0 2.051276 -14.321785 -1.935858 96 1 0 2.869625 -12.731715 3.610803 97 1 0 0.077431 -10.557395 2.569144 98 1 0 0.154093 -11.867738 3.746965 99 1 0 1.457296 -10.686564 3.662550 100 6 0 -3.755715 -13.330139 -1.652198 101 1 0 -3.981433 -14.267230 0.268515 102 1 0 -2.644887 -14.081986 2.073648 103 1 0 -0.916161 -13.897576 1.745004 104 1 0 -1.858060 -12.521718 2.307819 105 1 0 -3.227432 -12.245702 -3.427122 106 1 0 -1.416966 -9.911232 -2.720985 107 1 0 0.031842 -10.881972 -2.523729 108 1 0 -1.112517 -11.262594 -3.813001 109 6 0 4.459869 -14.557493 2.339562 110 6 0 -4.980543 -13.977780 -2.251964 111 1 0 4.267950 -15.636896 2.327352 112 1 0 5.363450 -14.387555 1.743005 113 1 0 4.679986 -14.269598 3.371165 114 1 0 -4.769497 -15.006400 -2.570373 115 1 0 -5.801180 -14.027568 -1.529107 116 1 0 -5.333925 -13.429647 -3.129998 117 6 0 3.104596 -3.044706 0.110503 118 6 0 -3.104596 3.044706 0.110503 119 1 0 3.098231 -3.911926 -0.516226 120 1 0 -3.098231 3.911926 -0.516226 121 1 0 3.817990 -2.340039 -0.262878 122 1 0 -3.817990 2.340039 -0.262878 123 1 0 -3.701524 2.602249 0.880443 124 1 0 3.701524 -2.602249 0.880443 125 6 0 0.534992 -11.537299 -1.192934 126 6 0 -0.534992 11.537299 -1.192934 127 7 0 1.098068 -11.582418 -2.308017 128 7 0 -1.098068 11.582418 -2.308017 ---------------------------------------------------------------------

Total Energy, E(TD-HF/TD-KS) = -3460.96088133

S24

1) Sun, Y.; Ross, N.; Zhao, S. B.; Huszarik, K.; Jia, W. L.; Wang, R. Y.; Macartney, D.; Wang, S.; J. Am. Chem. Soc. 2007, 129, 7510.

S25