a theoretical study of the reaction pathways of organozinc ... · web viewelectronic absorption...

D-A-D type dinitriles with vapor-dependent luminescence

in solid state

Taniyuki Furuyama,*ab Junichi Shinozaki,a Thiago Teixeira Tasso,b Hajime Maeda,a

Masahito Segia and Nagao Kobayashi*bc

a Graduate School of Natural Science and Technology, Kanazawa University

[email protected]

b Department of Chemistry, Graduate School of Science, Tohoku University

c Faculty of Textile Science and Technology, Shinshu University

[email protected]

Supporting information

Table of Contents

General Comments and Crystallographic data collection S–1

Additional Experimental Results S–5

Full Experimental Procedures S–15

Full Computational Details S–22

References S–28

General Comments

Unless otherwise noted, solvents and reagents were purchased from Tokyo Kasei Co. and Wako

Chemicals Co. and were used after appropriate purification (distillation or recrystallization).

Electronic absorption spectra were recorded on a JASCO V-570 spectrophotometer. NMR spectra

were obtained on a JEOL ECA-500 spectrometer. Unless otherwise noted, samples were recorded in

CDCl3. Chemical shifts are expressed in δ (ppm) values, and coupling constants are expressed in hertz

(Hz). 1H and 13C NMR spectra were referenced to the residual solvent as an internal standard. The

following abbreviations are used: s = singlet, d = doublet, and m = multiplet. High-resolution mass

spectra (HRMS) were recorded on a JEOL JMS-700 spectrometer. Fluorescence spectra in solutions were

recorded on a JASCO FP-8500 spectrometer. Fluorescence quantum yields were measured by using 9,10-

diphenylanthracene (FL = 0.90 in cyclohexane) as a standard.i Fluorescence spectra in solid-state and

absolute fluorescence quantum yields were recorded on a JASCO FP-6600 spectrometer with an

integration sphere ILF-533. Powder X-Ray diffraction (PXRD) data were collected using a Rigaku

SmartLab system diffractmeter with a CuK source. The simulated patterns were obtained from single-

crystal X-ray analysis.

Crystallographic data collection

A plate shaped and orange single crystal of 1THF 0.40 × 0.40 × 0.05 mm, was selected for

measurements. The diffraction data were collected using a Bruker APEXIII CCD diffractometer with

Bruker Helios multilayered confocal mirror monochromatized CuK radiation (λ = 1.54178 Å) at –

183°C. The structures were solved by a direct method (SIR2014) ii and refined using a full-matrix least

square technique (SHELXL-2014).iii Yadokari-XG 2009 software was used as a GUI for SHELXL-2014. iv

All non-hydrogen atoms were refined anisotropically. Positions of all hydrogen atoms were calculated

geometrically, and refined by applying riding models. The one styryl group on the dinitrile core was

severely disordered despite the low measurement temperature. Therefore, the structure was refined under

thermally and positionally restrained conditions, using DFIX, SIMU, ISOR, and DELU commands.

CCDC-1557597 and 1557596 contains the supplementary crystallographic data for 1THF and

1CHCl3, respectively. Its data can be obtained free of charge from Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

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The diffraction data of 1CHCl3 were collected under the same conditions. A part of dinitrile 1

was finely refined while some high electron density remained around disordered chloroforms in the

difference map. We could not resolve the density into a chemically reasonable pattern. The remained

density may be assigned to disordered chloroforms so that the problem only marginally affects the PXRD

simulated pattern.

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Table S1. Crystal data and structure refinement for 1THF.

Empirical formula C82H70N2O2.50

Formula weight 1123.40

Temperature 90 K

Wavelength 1.54178 Å

Crystal system Triclinic

Space group P–1 (No. 2)

Unit cell dimensions a = 9.5072(7) Å = 98.679(4)°

b = 13.1658(10) Å = 90.440(3)°

c = 25.4740(19) Å = 94.392(4)°

Volume 3142.2(4) Å3

Z 2

Density (Calcd.) 1.187 Mg/m3

Absorption coefficient 0.543 mm–1

F(000) 1192

Crystal size 0.40 x 0.40 x 0.05 mm3

Theta range for data collection 3.587 to 70.796°

Index ranges -11<=h<=11, -16<=k<=15, -30<=l<=31

Reflections collected 36825

Independent reflections 11108 [R(int) = 0.0451]

Completeness to theta = 25.00° 93.0%

Refinement method Full-matrix least-squares on F2

Data / restraints /parameters 11108 / 192 / 866

Goodness-of-fit on F2 1.117

Final R indices [I > 2sigma(I)] R1 = 0.0973, wR2 = 0.2171

R indices (all data) R1 = 0.1110, wR2 = 0.2250

Largest diff. peak and hole 0.612 and -0.419 e.Å-3

CCDC No. 1557597

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Table S2. Crystal data and structure refinement for 1CHCl3.

Empirical formula C73H53Cl9N2

Formula weight 1301.24

Temperature 90 K

Wavelength 1.54178 Å

Crystal system Triclinic

Space group P–1 (No. 2)

Unit cell dimensions a = 9.4643(4) Å = 98.837(2)°

b = 13.3753(6) Å = 90.512(2)°

c = 25.1104(12) Å = 94.674(3)°

Volume 3129.8(2) Å3

Z 2

Density (Calcd.) 1.381 Mg/m3

Absorption coefficient 4.044 mm–1

F(000) 1340

Crystal size 0.30 x 0.30 x 0.05 mm3

Theta range for data collection 3.356 to 66.596°

Index ranges -11<=h<=11, -15<=k<=15, -29<=l<=29

Reflections collected 31670

Independent reflections 10600 [R(int) = 0.0501]

Completeness to theta = 25.00° 95.9%

Refinement method Full-matrix least-squares on F2

Data / restraints /parameters 10600 / 388 / 897

Goodness-of-fit on F2 2.087

Final R indices [I > 2sigma(I)] R1 = 0.1383, wR2 = 0.4268

R indices (all data) R1 = 0.1546, wR2 = 0.4534

Largest diff. peak and hole 2.502 and -1.769 e.Å-3

CCDC No. 1557596

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Additional Experimental and Computational Results

Scheme S1. Synthesis of 1 and 2. Reagents and conditions: (i) KCN (1.3 eq), 18-crown-6 (0.5 eq),

CH3CN, rt, 20 h, 77%; (ii) 5 (0.74 eq), Pd(OAc)2 (5 mol%), PPh3 (12 mol%), Et3N, 100°C, 10 h, 51%;

(iii) I2 (1.0 eq), MeONa (2.0 eq), MeOH/Et2O, rt, 12 h, 20%; (iv) trimethylsilylacetylene (0.95 eq),

PdCl2(PPh3)2 (10 mol%), CuI (10 mol%), PPh3 (50 mol%), THF/Et3N, 70°C, 24 h; (v) KOH (6 eq),

MeOH/THF, rt, 3 h, 47% (two steps); (vi) I2 (1.0 eq), MeONa (2.0 eq), MeOH/Et2O, rt, 12 h, 90%; (vii)

PdCl2(PPh3)2 (20 mol%), CuI (20 mol%), PPh3 (50 mol%), THF/Et3N, 70°C, 24 h, 17%.

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Fig. S1. 1H NMR spectra of CDCl3 solution of 1 under UV (365 nm) irradiation.

Fig. S2. Detailed packing diagram of 1THF. Hydrogen atoms are omitted for clarity. 1 and THF

molecules were described with wireframe and ball and stick model, respectively.

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Fig. S3. Detailed packing diagram of TPE-CN2. Hydrogen atoms are omitted for clarity. TPE-CN2 and

THF molecules were described with wireframe and ball and stick model, respectively. Data was taken

from CCDC 1034202 (Tasso et al. Chem. Eur. J. 2015, 21, 4817.).

Fig. S4. Absorption and fluorescence spectra for (a) 1 and (b) 2 in different solvents. (c) Lippert-Mataga

plots for 1 and 2. Excited at 390 nm.

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Table S3. Absorption and emission wavelength maxima (abs and em) and fluorescence quantum yields

(F) of 1 and 2 in different solvents. Excited at 390 nm.

Compound CH2Cl2 CHCl3 THF Et2O Toluene Benzene

1abs/nm 440 447 433 429 444 444em/nm 598 593 587 562 562 562F/% 0.06 0.53 0.38 3.3 6.1 5.0

2abs/nm 411 419 401 402 414 412em/nm 528 585 554 560 548 550F/% 0.01 0.18 0.03 1.6 9.0 7.1

Fig. S5. Partial molecular energy diagram and orbitals of 1 and 2 (top) and their calculated absorption

spectra (bottom). Blue and red plots indicate occupied and unoccupied MOs, respectively. Calculations

were performed at the B3LYP/6-31G* level.

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Fig. S6. Fluorescence spectra of a) 1 and b) 2 and fluorescence intensities at each peak of c) 1 and d) 2 in

water/THF mixtures. Excitation at 440 and 410 nm for 1 and 2, respectively. c = 5.0 M.

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Fig. S7. Selected bond distances (Å) and torsion angles (degree) of (a) calculated optimized structure

(B3LYP/6-31G*) of 1, the X-ray structure of (b) 1THF and (c) 1CHCl3.

Fig. S8. Writing/erasing process on a filter paper coated with 1 powder. Photos were taken under UV

light (365 nm). The Chinese characters “金沢大” for “Kanazawa University” were written by scratching

the paper with a spatula.

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Fig. S9. Experimental XRD patterns for ground and dried (a) 1 (b) 2 and upon fuming the ground powder

with toluene for 30 min.

Fig. S10. Fluorescence spectra of ground 1 and powders after exposure to various solvents.

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Fig. S11. Experimental XRD patterns for ground and dried 2 and upon fuming the ground powder with

toluene or dichloromethane for 30 min.

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Fig. S12. Experimental XRD patterns for ground and dried 1 and upon fuming the ground powder with

various solvents for 30 min.

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Fig. S13. Detailed packing diagram of 1CHCl3. Hydrogen atoms are omitted for clarity. 1 and CHCl3

molecules were described with a wireframe and ball and stick model, respectively.

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Full Experimental Procedures

Compound 5 was synthesized according to published procedures.v

4-(Cyanomethyl)styrene (3)vi

A mixture of 4-(chloromethyl)styrene (503 mg, 3.29 mmol), KCN (279 mg, 4.29 mmol) and 18-

crown-6 (492 mg, 1.86 mmol) in CH3CN was stirred for 20 h and concentrated in vacuo. The residue was

dissolved in Et2O and extracted with Et2O. The organic layer was washed with brine and dried over

Na2SO4, filtered and concentrated in vacuo. The product was purified by silica gel column

chromatography. Title compound was obtained as a yellow oil (349 mg, 77%). 500 MHz 1H NMR

(CDCl3): = 7.40 (d, 2H, J = 8.0 Hz), 7.29-7.25 (m, 2H), 6.70 (dd, 1H, J = 17.5, 11 Hz), 5.75 (d, 1H, J =

17.5 Hz), 5.28 (d, 1H, J = 11 Hz), 3.73 (s, 2H).

Compound 4

A mixture of 5 (2.07 g, 5.05 mmol), 3 (0.984 g, 6.87 mmol), Pd(OAc)2 (65 mg, 0.29 mmol),

PPh3 (200 mg, 0.76 mmol) in 8 mL of Et3N was stirred for 10 h at 100°C. The mixture was quenched

with water and extracted with CHCl3. The organic layer was washed with brine and dried over Na2SO4,

filtered and concentrated in vacuo. The product was purified by silica gel column chromatography. Title

compound was obtained as a pale yellow solid (899 mg, 37%). 500 MHz 1H NMR (CDCl3): = 7.47 (d,

2H, J = 8.0 Hz), 7.29 (d, 2H, J = 8.0 Hz), 7.25 (d, 2H, J = 7.5 Hz), 7.14-7.01 (m, 19H), 3.75 (s, 2H). 125

MHz 13C NMR (CDCl3): = 143.64, 143.57, 140.5, 137.3, 131.8, 131.4, 131.3, 129.2, 128.8, 128.2,

127.8, 127.68, 127.61, 127.2, 127.0, 126.51, 126.49, 126.45, 125.9, 117.8, 23.4.

HRMS-FAB Calcd for C36H27N ([M]+): 473.2143, Found: 473.2126.

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Compound 1

Sodium methoxide (4 mmol) – methanol solution was slowly added to a solution of 4 (1.0 g,

2.12 mmol) and I2 (0.51 g, 2.01 mmol) in dry diethyl ether at –78°C. The reaction mixture was stirred for

12 h at rt. The crude product was filtered and washed with water and methanol. The residue was purified

by silica gel column chromatography. The pure 1 was obtained by size-exculsion chromatography

(JAIGEL-2H and 1H, CHCl3). Title compound was obtained as an orange solid (200 mg, 20%). 500 MHz

1H NMR (CDCl3): = 7.84 (d, 4H, J = 8.5 Hz), 7.60 (d, 4H, J = 9.0 Hz), 7.29 (d, 4H, J = 8.0 Hz), 7.15-

7.01 (m, 38H). 125 MHz 13C NMR (CDCl3): = 144.1, 143.6, 143.5, 141.4, 140.9, 140.4, 134.6, 131.8,

131.44, 131.40, 131.35, 131.33, 130.8, 129.2, 127.8, 127.7, 127.6, 126.9, 126.7, 126.6, 126.56, 126.51,

126.2, 123.7, 117.0.

HRMS-FAB Calcd for C72H50N2 ([M]+): 942.3974, Found: 942.3997.

Compound 7vii

A solution of compound 5 (2.15 g, 5.23 mmol) and (trimethylsilyl)acetylene (0.495 g, 5.04 mmol)

were added to a solution of PdCl2(PPh3)2 (350 mg, 0.49 mmol), CuI (95 mg, 0.50 mmol) and PPh3 (657

mg, 2.51 mmol) in 50 mL of THF/triethylamine (10/1). After the mixture was stirred for 24 h at 70°C,

quenched with water, filtered to remove insoluble residues and extracted with CHCl 3. The organic layer

was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product 6 was

dissolved in THF, then a solution of KOH (1.50 g, 26.7 mmol) in 15 mL of methanol was added. After the

S-16

mixture was stirred for 3 h, quenched with water and extracted with CHCl3. The organic layer was

washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The product was purified by

silica gel column chromatography. Title compound was obtained as a yellow solid (850 mg, 47%). 400

MHz 1H NMR (CDCl3): = 7.23 (d, 2H, J = 8.5 Hz), 7.13-6.97 (m, 17H), 3.04 (s, 1H).

Compound 8viii

The procedure described compound 1 was used with 4-bromophenylacetonitrile to give title

compound as a white solid (90%). 500 MHz 1H NMR (CDCl3): = 7.70 (m, 8H).

Compound 2

A solution of compound 7 (330 mg, 0.92 mmol) and 8 (378 mg, 0.48 mmol) were added to a

solution of PdCl2(PPh3)2 (90 mg, 0.12 mmol), CuI (48 mg, 0.12 mmol) and PPh3 (190 mg, 0.60 mmol) in

20 mL of THF/triethylamine (10/1). After the mixture was stirred for 24 h at 70°C, quenched with water,

filtered to remove insoluble residues and extracted with CHCl3. The organic layer was washed with brine,

dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by silica gel column

chromatography. The pure 2 was obtained by size-exculsion chromatography (JAIGEL-2H and 1H,

CHCl3). Title compound was obtained as a yellow solid (77 mg, 17%). 400 MHz 1H NMR (CDCl3): =

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7.83 (d, 4H, J = 8.1 Hz), 7.63 (d, 4H, J = 8.8 Hz), 7.30 (d, 4H, J = 8.5 Hz), 7.11-7.05 (m, 34H). 125 MHz

13C NMR (CDCl3): = 144.7, 143.4, 143.3, 143.2, 141.9, 140.1, 132.2, 131.5, 131.4, 131.3, 131.26,

131.20, 131.1, 128.7, 127.8, 127.7, 127.6, 127.2, 126.8, 126.7, 126.6, 124.4, 120.2, 116.5, 93.4, 88.6.

HRMS-FAB Calcd for C72H46N2 ([M]+): 938.3661, Found: 938.3656.

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Figure S14. 1H (top) and 13C (bottom) NMR spectra of 4 in CDCl3.

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Full Computational Details

Computational Details

Geometry optimization for all molecules was performed at the DFT level, by means of the hybrid

Becke3LYPix (B3LYP) functional as implemented in Gaussian 2009.x The 6-31G(d) basis set was used for

the all atoms. After the geometry optimization, the time-dependent (TD) DFT calculationsxi were

performed to evaluate the stick absorption spectrum employing the same level and basis set. All

stationary points were optimized without any symmetry assumptions and characterized by normal

coordinate analysis at the same level of the theory (the number of imaginary frequency, Nimag, 0).

Cartesian Coordinates and Total Electron Energies

1SCF Done: E(RB3LYP) = -2883.16010275 A.U. --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0 -0.025802 1.851918 -1.133920 2 6 0 -0.473932 0.559718 -0.696485 3 6 0 0.454585 -0.393033 -0.339263 4 6 0 1.928938 -0.234481 -0.323293 5 6 0 -1.949020 0.406516 -0.695509 6 6 0 0.007042 -1.687493 0.091839 7 7 0 0.259776 2.917539 -1.506534 8 7 0 -0.277950 -2.755802 0.457125 9 6 0 2.560861 0.968499 0.038980 10 6 0 3.946203 1.063138 0.052254 11 6 0 4.770971 -0.027941 -0.285710 12 6 0 4.130005 -1.235659 -0.633356 13 6 0 2.748272 -1.338808 -0.640840 14 6 0 -3.978605 -0.884341 -1.025538 15 6 0 -2.592797 -0.793736 -1.045535 16 6 0 -2.757447 1.514811 -0.364219 17 6 0 -4.139070 1.415427 -0.337932 18 6 0 -4.791410 0.206743 -0.659833 19 6 0 6.221150 0.143765 -0.242365 20 6 0 7.156747 -0.801904 -0.482122 21 6 0 -6.242327 0.035026 -0.643618 22 6 0 -7.158447 0.946961 -0.248351 23 6 0 8.608062 -0.638256 -0.431256 24 6 0 -8.610449 0.785771 -0.217050 25 6 0 9.250969 0.593085 -0.187805 26 6 0 10.634321 0.682942 -0.133780 27 6 0 11.452278 -0.448820 -0.324019 28 6 0 10.814416 -1.671557 -0.598653 29 6 0 9.427936 -1.764110 -0.639856 30 6 0 -10.666452 -0.464675 -0.603708 31 6 0 -9.284273 -0.365535 -0.674519 32 6 0 -9.399156 1.835374 0.292431 33 6 0 -10.784756 1.741529 0.350785 34 6 0 -11.452110 0.580328 -0.077769 35 6 0 12.940608 -0.353443 -0.300059 36 6 0 13.631422 -1.061791 -1.421944 37 6 0 13.624096 0.321285 0.674362

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38 6 0 15.079994 0.640055 0.563655 39 6 0 12.975811 0.790834 1.936472 40 6 0 15.611523 1.236605 -0.592881 41 6 0 16.964523 1.563460 -0.672755 42 6 0 17.817193 1.299460 0.401397 43 6 0 17.302105 0.716077 1.561325 44 6 0 15.946610 0.400997 1.645504 45 6 0 15.293856 -2.650916 -2.223688 46 6 0 14.878236 -2.443063 -3.540637 47 6 0 13.832823 -1.553665 -3.799971 48 6 0 13.209161 -0.879383 -2.750879 49 6 0 14.677604 -1.967253 -1.176178 50 6 0 13.188964 2.100050 2.404736 51 6 0 12.186021 -0.072185 2.715918 52 6 0 11.611052 0.364649 3.908655 53 6 0 11.811839 1.674920 4.348404 54 6 0 12.603744 2.541167 3.590816 55 6 0 -12.940664 0.497138 -0.031110 56 6 0 -13.649554 1.719621 -0.522380 57 6 0 -13.608218 -0.603550 0.431187 58 6 0 -12.927219 -1.710827 1.168686 59 6 0 -15.079520 -0.789420 0.244797 60 6 0 -13.290789 2.309291 -1.747557 61 6 0 -14.647053 2.342153 0.247178 62 6 0 -15.277413 3.502380 -0.201356 63 6 0 -14.925459 4.064606 -1.430265 64 6 0 -13.928997 3.462601 -2.202187 65 6 0 -17.259986 -1.382448 1.157146 66 6 0 -15.889793 -1.186381 1.323816 67 6 0 -15.683242 -0.628553 -1.014330 68 6 0 -17.051398 -0.837081 -1.184237 69 6 0 -17.847071 -1.208929 -0.098407 70 6 0 -12.558413 -4.093784 1.520297 71 6 0 -11.702915 -3.816888 2.589354 72 6 0 -11.467737 -2.490073 2.956467 73 6 0 -12.072660 -1.448762 2.253629 74 6 0 -13.172938 -3.052693 0.825821 75 1 0 1.974121 1.829342 0.334916 76 1 0 4.407248 2.003041 0.345057 77 1 0 4.718437 -2.107659 -0.900876 78 1 0 2.288944 -2.286658 -0.904607 79 1 0 -4.449277 -1.823450 -1.305324 80 1 0 -2.015478 -1.656344 -1.354695 81 1 0 -2.289528 2.463006 -0.117459 82 1 0 -4.718767 2.292916 -0.069560 83 1 0 6.546314 1.148005 0.023795 84 1 0 6.829305 -1.810159 -0.731804 85 1 0 -6.583710 -0.943521 -0.976743 86 1 0 -6.810348 1.916850 0.104270 87 1 0 8.662778 1.495113 -0.047362 88 1 0 11.098867 1.645548 0.053839 89 1 0 11.415911 -2.558774 -0.773143 90 1 0 8.962959 -2.727487 -0.837219 91 1 0 -11.155432 -1.363200 -0.965924 92 1 0 -8.721935 -1.191837 -1.099263 93 1 0 -8.910065 2.739806 0.647407 94 1 0 -11.362364 2.574702 0.740226 95 1 0 14.954677 1.445628 -1.431343 96 1 0 17.352164 2.029276 -1.575035 97 1 0 18.872114 1.552767 0.338027 98 1 0 17.955848 0.510210 2.404958 99 1 0 15.550613 -0.040562 2.555661 100 1 0 16.098210 -3.349816 -2.009434 101 1 0 15.360080 -2.974275 -4.357129 102 1 0 13.498756 -1.387296 -4.820851 103 1 0 12.389007 -0.197879 -2.959212 104 1 0 15.005616 -2.133105 -0.154727

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105 1 0 13.814822 2.774962 1.827637 106 1 0 12.027335 -1.092573 2.381171 107 1 0 11.008330 -0.321873 4.497506 108 1 0 11.361940 2.015550 5.277139 109 1 0 12.771066 3.561356 3.926491 110 1 0 -12.508190 1.853199 -2.347599 111 1 0 -14.925662 1.910135 1.203327 112 1 0 -16.042986 3.969423 0.412758 113 1 0 -15.418490 4.967551 -1.780425 114 1 0 -13.644475 3.893938 -3.158459 115 1 0 -17.869078 -1.675978 2.008231 116 1 0 -15.438142 -1.335197 2.300595 117 1 0 -15.070962 -0.339992 -1.862921 118 1 0 -17.495480 -0.712072 -2.168371 119 1 0 -18.913754 -1.369221 -0.230815 120 1 0 -12.752151 -5.122994 1.229330 121 1 0 -11.229818 -4.628153 3.136152 122 1 0 -10.814616 -2.263927 3.795268 123 1 0 -11.887000 -0.419804 2.545685 124 1 0 -13.847637 -3.275473 0.004006 ---------------------------------------------------------------------

TD–DFT outputHOMO: 248, LUMO: 249 Excited State 1: Singlet-A 2.1655 eV 572.54 nm f=1.4663 <S**2>=0.000 248 -> 249 0.70085 This state for optimization and/or second-order correction. Total Energy, E(TD-HF/TD-KS) = -2883.08052234 Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.3311 eV 531.86 nm f=0.0039 <S**2>=0.000 247 -> 249 0.70413


Excited State 4: Singlet-A 3.0406 eV 407.76 nm f=0.0023 <S**2>=0.000 245 -> 249 0.66296 248 -> 250 0.21575

Excited State 5: Singlet-A 3.1788 eV 390.04 nm f=0.0672 <S**2>=0.000 245 -> 249 -0.21338 247 -> 251 -0.21620 248 -> 250 0.62991

Excited State 6: Singlet-A 3.2108 eV 386.15 nm f=0.8468 <S**2>=0.000 246 -> 249 0.11376 247 -> 250 0.56214 248 -> 251 -0.38484



Excited State 9: Singlet-A 3.5973 eV 344.66 nm f=0.0083 <S**2>=0.000 240 -> 249 -0.16809 242 -> 249 0.17376 244 -> 249 0.65181

Excited State 10: Singlet-A 3.6097 eV 343.48 nm f=0.0011 <S**2>=0.000 239 -> 249 -0.15334 241 -> 249 -0.29125 243 -> 249 0.61035

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2SCF Done: E(RB3LYP) = -2880.66338602 A.U. --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0 -12.345620 4.657879 -0.813279 2 6 0 -12.070640 3.596343 -1.678097 3 6 0 -12.558327 2.319761 -1.400859 4 6 0 -13.332949 2.076403 -0.253501 5 6 0 -13.620521 3.160098 0.595925 6 6 0 -13.122680 4.433970 0.325746 7 6 0 -13.890518 0.719787 0.034227 8 6 0 -15.349321 0.699823 0.358770 9 6 0 -13.127695 -0.414768 -0.001756 10 6 0 -11.637139 -0.382220 -0.068444 11 6 0 -13.720995 -1.787538 0.017630 12 6 0 -13.220056 -2.769077 0.891447 13 6 0 -13.751781 -4.058014 0.902004 14 6 0 -14.781824 -4.400071 0.022829 15 6 0 -15.274794 -3.441800 -0.865537 16 6 0 -14.750359 -2.149811 -0.867888 17 6 0 -10.942600 -1.215215 -0.966528 18 6 0 -9.555182 -1.212460 -1.028049 19 6 0 -8.801063 -0.388241 -0.167158 20 6 0 -9.490661 0.428306 0.752967 21 6 0 -10.878669 0.428981 0.796132 22 6 0 -16.265306 1.415568 -0.433016 23 6 0 -17.625250 1.423387 -0.125958 24 6 0 -18.096500 0.734617 0.994090 25 6 0 -17.195639 0.037754 1.802439 26 6 0 -15.837509 0.019410 1.487675 27 6 0 -7.380404 -0.386426 -0.221332 28 6 0 -6.163748 -0.383163 -0.270710 29 6 0 -4.745052 -0.378725 -0.330217 30 6 0 -3.985378 0.394093 0.573254 31 6 0 -2.599233 0.399070 0.513963 32 6 0 -1.914602 -0.369697 -0.446796 33 6 0 -2.674542 -1.120334 -1.366555 34 6 0 -4.059568 -1.134933 -1.305086 35 6 0 -0.436509 -0.378252 -0.532544 36 6 0 18.186633 -0.182737 0.657568 37 6 0 17.297258 0.462843 1.519428 38 6 0 15.922787 0.383811 1.299186 39 6 0 15.406613 -0.345043 0.213781 40 6 0 16.313507 -1.008270 -0.632365 41 6 0 17.688519 -0.918524 -0.420160 42 6 0 13.934057 -0.468737 -0.008424 43 6 0 13.451551 -1.863569 -0.244447 44 6 0 13.093737 0.610304 -0.002890 45 6 0 11.608194 0.472381 0.039229 46 6 0 13.587637 2.021273 -0.043232 47 6 0 14.532338 2.436892 -0.997268 48 6 0 14.959855 3.762986 -1.050607 49 6 0 14.453170 4.703035 -0.150504 50 6 0 13.506590 4.307374 0.797278 51 6 0 13.071018 2.983611 0.842841 52 6 0 10.974043 -0.366433 0.974461 53 6 0 9.589909 -0.460290 1.036207 54 6 0 8.779503 0.284420 0.154302 55 6 0 9.408852 1.133686 -0.779365 56 6 0 10.793512 1.232061 -0.822237 57 6 0 12.619415 -2.172186 -1.334486 58 6 0 12.201262 -3.481681 -1.568101 59 6 0 12.604450 -4.511577 -0.715508 60 6 0 13.440297 -4.222426 0.365882 61 6 0 13.868820 -2.915055 0.591447

S-25

62 6 0 7.362219 0.187850 0.212029 63 6 0 6.148552 0.103364 0.262789 64 6 0 4.733511 0.002604 0.324344 65 6 0 3.918361 0.672856 -0.611995 66 6 0 2.535848 0.573099 -0.551339 67 6 0 1.910452 -0.202286 0.443929 68 6 0 2.724192 -0.849110 1.395975 69 6 0 4.106318 -0.759165 1.333549 70 6 0 0.437329 -0.321627 0.531748 71 6 0 0.083996 -0.511598 -1.864009 72 7 0 0.426202 -0.647801 -2.968651 73 6 0 -0.074305 -0.437561 1.868324 74 7 0 -0.407454 -0.552366 2.978142 75 1 0 -11.963827 5.652250 -1.028647 76 1 0 -11.478047 3.762134 -2.573976 77 1 0 -12.342888 1.499954 -2.079127 78 1 0 -14.234995 2.996313 1.476738 79 1 0 -13.346279 5.253954 1.003276 80 1 0 -12.411535 -2.513863 1.571018 81 1 0 -13.357969 -4.797008 1.594966 82 1 0 -15.191965 -5.406419 0.025416 83 1 0 -16.067784 -3.700776 -1.562243 84 1 0 -15.138217 -1.409739 -1.560867 85 1 0 -11.504624 -1.867055 -1.628863 86 1 0 -9.038525 -1.850085 -1.738847 87 1 0 -8.923593 1.056255 1.433211 88 1 0 -11.389858 1.064007 1.512199 89 1 0 -15.904218 1.964299 -1.298294 90 1 0 -18.316854 1.972495 -0.759666 91 1 0 -19.155271 0.746699 1.238765 92 1 0 -17.549810 -0.490848 2.683618 93 1 0 -15.143293 -0.523988 2.120924 94 1 0 -4.497533 0.998465 1.314785 95 1 0 -2.046364 1.022584 1.207056 96 1 0 -2.169164 -1.702784 -2.130772 97 1 0 -4.629079 -1.728674 -2.012681 98 1 0 19.257973 -0.119092 0.828376 99 1 0 17.673423 1.027238 2.368707 100 1 0 15.237614 0.887570 1.973700 101 1 0 15.932891 -1.593057 -1.465030 102 1 0 18.371498 -1.428471 -1.094647 103 1 0 14.930300 1.711904 -1.700434 104 1 0 15.687629 4.062795 -1.800127 105 1 0 14.787855 5.736120 -0.191639 106 1 0 13.102821 5.031263 1.500394 107 1 0 12.326186 2.686294 1.575928 108 1 0 11.580196 -0.946767 1.662352 109 1 0 9.119205 -1.107600 1.769718 110 1 0 8.797971 1.715445 -1.462815 111 1 0 11.259198 1.902738 -1.538262 112 1 0 12.304245 -1.377067 -2.003067 113 1 0 11.562235 -3.697636 -2.420304 114 1 0 12.276568 -5.531719 -0.896361 115 1 0 13.763996 -5.017398 1.032707 116 1 0 14.530053 -2.699543 1.426054 117 1 0 4.383830 1.280929 -1.380783 118 1 0 1.938307 1.120419 -1.271106 119 1 0 2.263811 -1.433517 2.186684 120 1 0 4.718452 -1.274320 2.066668 ---------------------------------------------------------------------

TD–DFT outputHOMO: 246, LUMO: 247 Excited State 1: Singlet-A 2.1665 eV 572.29 nm f=1.3045 <S**2>=0.000 246 -> 247 0.70110 This state for optimization and/or second-order correction.

S-26

Total Energy, E(TD-HF/TD-KS) = -2880.58376951 Copying the excited state density for this state as the 1-particle RhoCI density.




Excited State 5: Singlet-A 3.2858 eV 377.33 nm f=0.0027 <S**2>=0.000 245 -> 249 -0.28540 246 -> 248 0.63857

Excited State 6: Singlet-A 3.3147 eV 374.04 nm f=0.9900 <S**2>=0.000 244 -> 247 0.10270 245 -> 248 0.53664 246 -> 249 -0.42040

Excited State 7: Singlet-A 3.5288 eV 351.35 nm f=0.0224 <S**2>=0.000 240 -> 247 -0.13224 242 -> 247 0.53036 245 -> 248 -0.31467 246 -> 249 -0.29611

Excited State 8: Singlet-A 3.5395 eV 350.29 nm f=0.0316 <S**2>=0.000 242 -> 247 0.42496 245 -> 248 0.30337 246 -> 249 0.45677

Excited State 9: Singlet-A 3.5474 eV 349.50 nm f=0.0008 <S**2>=0.000 239 -> 247 -0.17556 241 -> 247 0.66347

Excited State 10: Singlet-A 3.5879 eV 345.57 nm f=0.0049 <S**2>=0.000 237 -> 247 -0.11355 240 -> 247 0.66384 242 -> 247 0.15234

S-27

References for Supporting Information

S-28

i Ie, Y.; Umemoto, Y.; Kaneda, T.; Aso, Y. Org. Lett. 2006, 8, 5381-5384.

ii Burla, M. C.; Caliandro, R.; Carrozzini, B.; Cascarano, G. L.; Cuocci, C.; Giacovazzo, C.; Mallamo, M.; Mazzone, A.;

Polidori, G. J. Appl. Cryst. 2015, 48, 306-309.

iii Sheldrick, G. M. Acta Crystallogr. C, Struct. Chem. 2015, 71, 3-8.

iv Yadokari-XG, Software for Crystal Structure Analyses, K. Wakita (2001); Release of Software (Yadokari-XG 2009)

for Crystal Structure Analyses, Kabuto, C.; Akine, S.; Nemoto, T.; Kwon, E. J. Cryst. Soc. Jpn. 2009, 51, 218-224.

v Yuan, W. Z.; Lu, P.; Chen, S.; Lam, J. W. Y.; Wang, Z.; Liu, Y.; Kwok, H. S.; Ma, Y.; Tang, B. Z. Adv. Mater. 2010, 22,

2159-2163.

vi Zhao, L.-J.; Kwong, C. K.-W.; Shi, M.; Toy, P. H. Tetrahedron 2005, 61, 12026-12032.

vii Wang, J.; Mei, J.; Zhao, E.; Song, Z.; Qin, A.; Sun, J. Z.; Tang, B. Z. Macromolecules 2012, 45, 7692-7703.

viii Furuyama, T.; Ogura, Y.; Yoza, K.; Kobayashi, N. Angew. Chem. Int. Ed. 2012, 51, 11110-11114.

ix (a) Becke, A. D. Phys. Rev. 1988, A38, 3098-3100. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377. (c) Becke,

A. D. J. Chem. Phys. 1993, 98, 5648-5652. (d) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785-788.

x Gaussian 09, Revision C.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman,

J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.;

Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;

Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.;

Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;

Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross,

J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;

Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg,

J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc.,

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xi (a) Bauernschmitt, R. d.; Ahlrichs, R. Chem. Phys. Lett. 1996, 256, 454-464. (b) Dreuw, A.; Head-Gordon, M. Chem.

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