Quenching of fluorescence as an indicator of donor ... · Quenching of fluorescence as an indicator of donor-strength in meso arylethynyl BODIPYs Rajneesh Misra,* Bhausaheb Dhokale,

S 1

Supporting Information

Quenching of fluorescence as an indicator of donor-strength in meso

arylethynyl BODIPYs

Rajneesh Misra,* Bhausaheb Dhokale, Thaksen Jadhav, Shaikh M. Mobin

*E-mail: [email protected]

Department of Chemistry,

Indian Institute of Technology Indore,

Indore- 452 017, India.

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2014

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Table of Contents

I. Crystallographic data······················································································S3

II. Photophysical Data·························································································S7

III. Electrochemical Data·····················································································S8

IV. Copies of 1H NMR, 13C NMR and HRMS Spectra of the New Compounds··················S13

V. Theoretical Calculations··············································································S37

References············································································································S58


S 3

Single Crystal X-ray Diffraction Studies.

Single crystal X-ray structural studies of 2d and 2e were performed on a CCD Agilent

Technologies (Oxford Diffraction) SUPER NOVA diffractometer. Data were collected at 150(2)

K using graphite-monochromated CuK\α radiation (λα = 1.5418 Å). The strategy for the Data

collection was evaluated by using the CrysAlisPro CCD software. The data were collected by the

standard 'phi-omega scan techniques, and were scaled and reduced using CrysAlisPro RED

software. The structures were solved by direct methods using SHELXS-97, and refined by full

matrix least-squares with SHELXL-97, refining on F2.1. The positions of all the atoms were

obtained by direct methods. All non-hydrogen atoms were refined anisotropically. The remaining

hydrogen atoms were placed in geometrically constrained positions, and refined with isotropic

temperature factors, generally 1.2Ueq of their parent atoms. The crystal structure, and dat

refinement parameters are summarized in Table 1. The CCDC numbers 967406, and 967407

contain the supplementary crystallographic data for 2d and 3e respectively. These data can be

obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge

Crystallographic Data Centre, 12 union Road, Cambridge CB21 EZ, UK; Fax: (+44) 1223-336-

033; or [email protected]).


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Table S1. Crystal structure and data refinement parameters

BODIPY 2d 2e Empirical formula C21 H13 B F2 N2 C21 H13 B F2 N2 Formula weight 342.14 342.14 Temperature/K 150(2) 150(2) Crystal system Orthorhombic Monoclinic Space group P212121 P2/c Unit cell dimensions a/Å a = 5.5995(2) a = 10.1059(3) α/° 90 90 b/ Å 13.5098(4) b = 10.4411(3) β/° 90 100.699(3) c/ Å 22.2683(8) 15.6091(5) γ/° 90 90 Volume/ Å3 1684.56(10) 1618.39(8) Z 4 4 Calculated density/ Mg/m3 1.349 1.404 Absorption coefficient/mm-1 0.779 0.811 F(000) 704 704

Crystal size/mm 0.21 x 0.18 x 0.13 0.33 x 0.26 x 0.19

θ range from data collection/° 3.83 to 72.10 4.23 to 72.16

Reflections collected/unique 11102 / 3269 [R(int) = 0.0166]

10226 / 3147 [R(int) = 0.0239]

Absorption correction Semi-empirical from equivalents

Semi-empirical from equivalents

Data/restraints/parameters 3269 / 0 / 236 3147 / 0 / 236 Goodness-of-fit on F2 1.023 1.090

Final R indices [I > 2σ (I)] R1 = 0.0281, wR2 = 0.0735

R1 = 0.0427, wR2 = 0.1244

R indices (all data) R1 = 0.0336, wR2 = 0.0788

R1 = 0.0519, wR2 = 0.1387

Largest diff. peak and hole/e Å-3 0.081 and -0.099 0.198 and -0.207

Absolute structure parameter 0.10(14) - CCDC number 967406 967407


S 5

Table S2. Selected torsional angles obtained from crystal structure and theoretical calculations

BODIPY 2d 2e Torsional angle 4.97 2.68 Theoretical torsional angle 0.23 13.43

Table S3. Distance and angle of intermolecular of interactions in the crystal structures.

Interaction Distance (Å) Angle of Interaction (°) 2d F(1)---H(7)-C(7) 2.355 131.08 F(1)---H(21)-C(21) 2.285 128.27 F(2)---H(9)-C(9) 2.627 119.94 C(17)-H(17)---π (pyrrolic) 3.044 π---π between two BODIPY units 3.383 2e F(1)---H(9)-C(9) 2.467 160.18 F(2)---H(18)-C(18) 2.527 156.97 π---π between two BODIPY units 3.384


S 6

Figure S1. Crystal structure of 2d

Figure S2. Crystal structure of 2e


S 7

Figure S3. Crystal structure packing of 2d.

The fluorescence quantum yields (ɸF)

The fluorescence quantum yields (ɸF) of compounds 2-6 were calculated by the steady-state

comparative method using Rhodamine 6G as a standard (ɸst = 0.88, ethanol).1

a c

b

a c

b

a

bc

a

bc

A

B

C

D


S 8

ɸF= ɸst × Su/Sst × Ast / Au × n2Du/n2

Dst ……………….. (Eq. 1)

Where ɸF is the emission quantum yield of the sample, ɸst is the emission quantum yield

of the standard, Ast and Au represent the absorbance of the standard and sample at the

excitation wavelength, respectively, while Sst and Su are the integrated emission band

areas of the standard and sample, respectively, and nDst and nDu the solvent refractive index

of the standard and sample, u and st refer to the unknown and standard, respectively.

Electrochemical Characterizations

Figure S4. CV and DPV plots of of meso-arylethynyl BODIPY 2a.

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

-80.0µ

-60.0µ

-40.0µ

-20.0µ

0.0

20.0µ

40.0µ

Potential Vc Fc/Fc+ (V)

DPV CV

Cur

rent

(A)


S 9

Figure S5. CV and DPV plots of of meso-arylethynyl BODIPY 2b.

Figure S6. CV and DPV plots of of meso-arylethynyl BODIPY 2c.

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5-60.0µ

-50.0µ

-40.0µ

-30.0µ

-20.0µ

-10.0µ

0.0

10.0µ

20.0µ


CV DPV

Cur

rent

(A)

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5-120.0µ

-100.0µ

-80.0µ

-60.0µ

-40.0µ

-20.0µ

0.0

20.0µ

40.0µ CV DPV

Cur

rent

(A)



S 10

Figure S7. CV and DPV plots of of meso-arylethynyl BODIPY 2d.

Figure S8. CV and DPV plots of of meso-arylethynyl BODIPY 2e.

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

-100.0µ

-80.0µ

-60.0µ

-40.0µ

-20.0µ

0.0

20.0µ

40.0µ


CV CPV

Cur

rent

(A)

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

-80.0µ

-60.0µ

-40.0µ

-20.0µ

0.0

20.0µ


CV DPV

Cur

rent

(A)


S 11

Figure S9. CV and DPV plots of of meso-arylethynyl BODIPY 2f.

Figure S10. CV and DPV plots of meso-arylethynyl BODIPY 2g.

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

-120.0µ

-100.0µ

-80.0µ

-60.0µ

-40.0µ

-20.0µ

0.0

20.0µ


CV DPV

Cur

rent

(A)

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

-100.0µ

-80.0µ

-60.0µ

-40.0µ

-20.0µ

0.0

20.0µ


CV DPV

Cur

rent

(A)


S 12

Figure S11. CV and DPV plots of meso-arylethynyl BODIPY 2h.

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

-50.0µ

-40.0µ

-30.0µ

-20.0µ

-10.0µ

0.0

10.0µ

20.0µ

30.0µ

40.0µ

50.0µ


CV DPV

Cur

rent

(A)


S 13

HRMS spectra of 2a


S 14

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.302.15 2.082.001.95 1.89

Chloroform-d

7.80

887.

6269

7.60

437.

3898

7.37

987.

2600

6.97

776.

9558

6.54

626.

5374

3.88

49

1.58

11

-0.0

002

7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5Chemical Shift (ppm)

2.15 2.082.001.95 1.89

Chloroform-d

6.53

746.

5462

6.95

586.

9777

7.26

00

7.37

987.

3898

7.60

437.

6269

7.80

88

N NB

FF

O

1H NMR spectra of 2a


S 15

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

Chloroform-d

162.

1704

143.

1415

136.

4704

134.

9539

128.

8443

128.

2537

114.

7877

112.

9869

107.

6865

84.4

143

77.4

808

77.3

642

77.1

600

76.8

465

55.6

887

160 155 150 145 140 135 130 125 120 115 110 105 100 95 90 85Chemical Shift (ppm)

84.4

143

107.

6865

112.

9869

114.

7877

128.

2537

128.

8443

134.

9539

136.

4704

143.

1415

162.

1704

N NB

FF

O

13C NMR spectra of 2a


S 16

HRMS spectra of 2b


S 17

1H NMR spectra of 2b

13 Oct 2013

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

6.11 2.27 2.072.00

Chloroform-d

Chloroform-d

-0.0

196

-0.0

114

-0.0

033

1.50

141.

5516

1.60

12

5.28

87

6.51

806.

5256

6.98

917.

01107.15

597.17

357.

2500

7.33

097.

3340

7.45

327.

4758

7.78

13

7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5Chemical Shift (ppm)

6.11 5.76 2.272.16 2.072.00

Chloroform-d

7.78

13 7.47

587.

4708

7.45

327.

4469

7.35

357.

3472 7.33

407.

3309

7.31

337.

3083

7.30

02

7.25

00

7.17

357.

1559

7.13

967.

1365

7.01

107.

0060

6.98

91

6.52

566.

5180

N

N NB

FF


S 18

13C NMR spectra of 2b

152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

Chloroform-d

150.

8041

146.

3057

142.

5655

136.

3246

134.

4509

129.

8504

128.

4141

126.

1467

125.

0895

120.

4526

118.

0029

117.

9737

112.

1338

109.

2977

85.5

808

77.4

735

77.3

569

77.1

600

76.8

392

150 145 140 135 130 125 120 115 110 105 100 95 90 85Chemical Shift (ppm)

85.5

808

109.

2977

112.

1338

118.

0029

120.

4526

125.

0895

126.

1467

128.

4141

129.

8504

134.

4509

136.

3246

142.

5655

146.

3057

150.

8041

N

N NB

FF


S 19

HRMS spectra of 2c


S 20

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

4.38 2.80 2.00

Chloroform-d

7.84

027.

7279

7.70

417.

6539

7.65

017.

6319

7.49

407.

4745

7.43

007.

4187

7.26

00

6.57

006.

5600

1.57

73

7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5Chemical Shift (ppm)

4.38 2.802.202.09 2.001.93

Chloroform-d

6.56

006.

5700

7.26

00

7.40

057.

4187

7.43

007.

4369

7.47

457.

4940

7.50

717.

5115

7.63

197.

6451

7.65

017.

6539

7.68

287.

7041

7.72

797.

7492

7.84

02

N NB

FF

1H NMR spectra of 2c


S 21

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

Chloroform-d

76.8

392

77.1

600

77.4

735

85.0

632

106.

1408

118.

4841

119.

7235

127.

2695

127.

5830

128.

4797

129.

1724

133.

3864

136.

6454

139.

7586

143.

6883

143.

9653

145 140 135 130 125 120 115 110 105 100 95 90 85Chemical Shift (ppm)

143.

9653

143.

6883

139.

7586

136.

6454

133.

3864

129.

1724

128.

4797

127.

5830

127.

5174

127.

2695

119.

7235

118.

4841

106.

1408

85.0

632

N NB

FF

13C NMR spectra of 2c


S 22

HRMS spectra of 2d


S 23

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

5.26 2.10 2.001.02

Chloroform-d

1.25

30

1.56

85

2.17

00

6.57

696.

5870

7.26

007.

4689

7.47

897.

5949

7.60

257.

6112

7.64

397.

6652

7.66

907.

8502

7.89

797.

9205

8.23

16

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6Chemical Shift (ppm)

5.26 2.10 2.001.771.141.02

Chloroform-d

6.57

696.

5870

7.26

00

7.46

897.

4789

7.57

937.

5874

7.59

497.

6025

7.60

697.

6112

7.64

397.

6476

7.66

527.

6690

7.85

027.

8784

7.89

797.

9123

7.92

05

8.23

16

2d

N NB

FF

1H NMR spectra of 2d


S 24

13C NMR spectra of 2d

13 Oct 2013


Chloroform-d

76.8

392

77.1

600

77.4

735

84.6

695

106.

5929

118.

2289

118.

5206

127.

4080

128.

2173

128.

4287

128.

8589

129.

2380

132.

9052

134.

1301

136.

7183

143.

7466

2d

N NB

FF

137.0 136.5 136.0 135.5 135.0 134.5 134.0 133.5 133.0 132.5 132.0 131.5 131.0 130.5 130.0 129.5 129.0 128.5 128.0 127.5 127.0Chemical Shift (ppm)

136.

7183

134.

1666

134.

1301

132.

9052 12

9.23

80

128.

8589 12

8.42

8712

8.21

7312

8.14

44

127.

5611

127.

4080


S 25

HRMS spectra of 2e


S 26

8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6Chemical Shift (ppm)

2.09 2.081.91 1.761.261.17 1.151.141.03

Chloroform-d

6.60

276.

6133

7.26

00

7.51

847.

5285

7.53

917.

5567

7.55

987.

5774

7.61

947.

6225

7.62

577.

6401

7.64

267.

6903

7.69

407.

7116

7.71

477.

7285

7.87

347.

9343

7.93

687.

9550

8.01

208.

0334

8.34

328.

3457

8.36

398.

3671


2.09 2.081.761.171.03

Chloroform-d

-0.0

497

-0.0

083

0.00

050.

0500

1.50

081.

5503

1.60

05

5.29

87

6.60

276.

6133

7.26

007.

5184

7.52

857.

5391

7.55

677.

5598

7.57

747.

6225

7.87

347.

9343

7.93

687.

9550

8.01

208.

3457

8.36

71

2e

N NB

FF

1H NMR spectra of 2e


S 27

13C NMR spectra of 2e


Chloroform-d

76.8

465

77.1

600

77.3

641

77.4

808

89.0

221

104.

4494

118.

6445

125.

4686

125.

6436

127.

2257

127.

4809

128.

1079

128.

9755

129.

2161

132.

0158

133.

2042

133.

4302

136.

6819

143.

7539

144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127Chemical Shift (ppm)

143.

7539

136.

6819

133.

4302

133.

3208

133.

2042

132.

0158

129.

2161

128.

9755

128.

1079

127.

4809

127.

2257


125.

6436

125.

4686

118.

6445

118.

6007

104.

4494

89.0

221

2e

N NB

FF


S 28

HRMS spectra of 2f


S 29

8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6Chemical Shift (ppm)

3.20 2.001.92 1.921.141.141.12 1.101.01 0.99

Chloroform-d

6.60

206.

6121

7.26

00

7.52

537.

5354

7.65

147.

6690

7.68

597.

6890

7.74

677.

7505

7.75

617.

7643

7.77

187.

7800

7.78

507.

7888

7.87

597.

9274

7.94

68

8.24

41

8.39

538.

4034

8.41

108.

4191

8.68

518.

7058

8.72

468.

7327

8.73

968.

7484


3.20 2.001.921.141.14 1.01

Chloroform-d

0.00

42

1.25

68

1.55

03

6.60

206.

6121

7.26

007.

5253

7.53

547.

6690

7.74

677.

7561

7.76

437.

7718

7.78

007.

8759

7.92

747.

9468

8.24

418.

6851

8.70

588.

7246

N NB

FF

1H NMR spectra of 2f


S 30


Chloroform-d

0.14

03

76.8

392

77.1

600

77.4

735

88.6

211

104.

6754

117.

6165

118.

6445

123.

0044

123.

3470

126.

4456

127.

4444

127.

6048

127.

8819

129.

2817

129.

3984

130.

3389

130.

5576

130.

8347

131.

5710

135.

6539

136.

7548

143.

8050

140 135 130 125 120 115 110 105 100 95 90Chemical Shift (ppm)

88.6

211

104.

6754

117.

6165

118.

6445

123.

0044

123.

3470

126.

4456

127.

4444

127.

6048

127.

8819

129.

2817

129.

3984

130.

3389

130.

5576

130.

8347

131.

5710

135.

6539

136.

7548

143.

8050

N NB

FF

13C NMR spectra of 2f


S 31

HRMS spectra of 2g


S 32


6.24 1.95 1.931.821.00

Chloroform-d

8.51

078.

2912

8.28

058.

2686

8.22

668.

1808

8.16

388.

0992

8.08

738.

0804

7.87

667.

5504

7.54

047.

2600

6.61

836.

6102

1.57

10

0.07

450.

0017

8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6Chemical Shift (ppm)

6.24 2.08 1.95 1.931.821.00

Chloroform-d

6.61

026.

6183

7.26

00

7.54

047.

5504

7.87

66

8.06

108.

0647

8.08

048.

0873

8.09

928.

1438

8.16

388.

1808

8.20

348.

2266

8.24

668.

2617

8.26

868.

2805

8.29

128.

2999

8.51

078.

5333

N NB

FF

1H NMR spectra of 2g


S 33


Chloroform-d

143.

4113

136.

6017

133.

6052

133.

4593

131.

2138

131.

0971

130.

9003

130.

1202

130.

0254

128.

9464

127.

3059

126.

9560

124.

7614

124.

1053

114.

8752

106.

3085

90.4

292

77.4

735

77.3

569

77.1

600

76.8

392

0.14

03

140 135 130 125 120 115 110 105 100 95 90Chemical Shift (ppm)

90.4

292

106.

3085

114.

8752

124.

1053

124.

5063

124.

7614

124.

9000

126.

8904

126.

9560

127.

3059

127.

6632

128.

9464

130.

0254

130.

1202

130.

9003

131.

0971

131.

2138

133.

4593

133.

6052

136.

6017

143.

4113

N NB

FF

13C NMR spectra of 2g


S 34

HRMS spectra of 2h


S 35

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

4.042.07 2.001.99 1.93

Chloroform-d

8.62

428.

5803

8.57

788.

5584

8.10

808.

0867

7.90

177.

7505

7.73

427.

7154

7.71

227.

6332

7.62

077.

6037

7.60

007.

5824

7.26

00

6.65

796.

6478

1.61

871.

5685

-0.0

008

8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7Chemical Shift (ppm)

4.042.152.07 2.001.99 1.931.10

Chloroform-d

6.64

786.

6579

7.26

00

7.57

997.

5824

7.59

627.

6000

7.60

377.

6207

7.63

327.

7122

7.71

547.

7285

7.73

427.

7373

7.75

057.

7536

7.90

17

8.08

678.

1080

8.55

848.

5778

8.58

038.

6242

N NB

FF

1H NMR spectra of 2h


S 36

13C NMR spectra of 2h

144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

Chloroform-d

143.

4113

136.

5434

134.

1228

132.

0303

131.

1700

129.

4713

128.

9682

128.

4798

127.

4882

126.

3144

126.

0301

118.

5789

114.

4669

103.

8297

95.8

900

77.4

808

77.3

642

77.1

600

76.8

392


127.

4882

128.

4798

128.

9682

129.

4713

131.

1700

132.

0303

134.

1228

136.

5434

143.

4113


95.8

900

103.

8297

114.

4669

118.

5789

126.

0301

126.

3144

127.

4882

128.

4798

128.

9682

129.

4713

2h

N NB

FF


S 37

DFT calculation data

Calculation method: B3LYP/6-31G(d) with Gaussian 09.2

BODIPY HOMO-1 HOMO LUMO LUMO+1

N NB

FF

O

N

N NB

FF

N NB

FF

N NB

FF

N NB

FF

N NB

FF

N NB

FF

N NB

FF The HOMO-1, HOMO, LUMO. LUMO+1 energy levels of the BODIPY dimmers


S 38

DFT Data for meso-arylethynyl BODIPY 2a

Standard orientation:

---------------------------------------------------------------------

Center Atomic Atomic Coordinates (Angstroms)

Number Number Type X Y Z

---------------------------------------------------------------------

1 6 0 1.423410 2.546303 -0.084649

2 1 0 0.373736 2.804655 -0.104308

3 6 0 2.516227 3.405004 -0.120820

4 1 0 2.504050 4.485052 -0.171706

5 6 0 3.668252 2.594270 -0.085738

6 1 0 4.710645 2.883147 -0.096311

7 7 0 3.323711 1.296967 -0.031347

8 5 0 4.312519 0.085600 0.101503

9 6 0 2.750879 -3.350862 -0.116326

10 6 0 1.601084 -2.570271 -0.081152

11 1 0 0.571999 -2.901411 -0.100030

12 6 0 2.020657 -1.219076 -0.028890

13 6 0 1.274508 -0.020201 -0.017372

14 6 0 1.935914 1.227758 -0.030535

15 7 0 3.410059 -1.191605 -0.029821

16 9 0 5.243621 0.117453 -0.918490

17 6 0 3.843832 -2.461859 -0.082434

18 1 0 4.903804 -2.677441 -0.092742

19 9 0 4.918299 0.107312 1.344634


S 39

20 1 0 2.813741 -4.429209 -0.165670

21 6 0 -0.135853 -0.068359 -0.014120

22 6 0 -1.354545 -0.107030 -0.006997

23 6 0 -2.771236 -0.152929 0.000978

24 6 0 -3.457285 -1.390005 0.006248

25 6 0 -3.531043 1.032224 0.004184

26 6 0 -4.839272 -1.432106 0.014196

27 1 0 -2.886372 -2.313112 0.004257

28 6 0 -4.921580 0.996852 0.012176

29 1 0 -3.019153 1.989455 0.000596

30 6 0 -5.585032 -0.239525 0.017155

31 1 0 -5.374405 -2.376124 0.018367

32 1 0 -5.476542 1.927575 0.014468

33 8 0 -6.932913 -0.391383 0.024920

34 6 0 -7.751444 0.772348 0.028916

35 1 0 -7.584530 1.381629 -0.868131

36 1 0 -8.780524 0.410509 0.035051

37 1 0 -7.574248 1.382714 0.923243

---------------------------------------------------------------------

Total Energy= -1103.1147262 HF

DFT data for meso-arylethynyl BODIPY 2b


---------------------------------------------------------------------



---------------------------------------------------------------------


S 40

1 6 0 -4.118253 -2.376357 -0.950875

2 1 0 -3.078004 -2.645663 -1.070740

3 6 0 -5.240062 -3.136649 -1.263282

4 1 0 -5.264518 -4.134683 -1.678775

5 6 0 -6.363444 -2.350585 -0.939891

6 1 0 -7.415145 -2.585039 -1.034957

7 7 0 -5.974510 -1.160598 -0.451491

8 5 0 -6.921601 -0.035552 0.094921

9 6 0 -5.246198 3.215547 1.049914

10 6 0 -4.122862 2.434624 0.800206

11 1 0 -3.083129 2.719339 0.883294

12 6 0 -4.587436 1.161817 0.391442

13 6 0 -3.880922 0.007703 -0.015967

14 6 0 -4.585321 -1.139991 -0.444755

15 7 0 -5.976672 1.179400 0.399002

16 9 0 -7.850947 0.312917 -0.866571

17 6 0 -6.368003 2.403720 0.791072

18 1 0 -7.420200 2.642147 0.869090

19 9 0 -7.532586 -0.459809 1.261411

20 1 0 -5.272629 4.246696 1.374483

21 6 0 -2.471439 0.008149 -0.014343

22 6 0 -1.251157 0.006686 -0.010149

23 6 0 0.163593 0.004515 -0.005799

24 6 0 0.890896 -1.147836 -0.376616

25 6 0 0.892432 1.154450 0.369382

26 6 0 2.275435 -1.150976 -0.375857


S 41

27 1 0 0.351350 -2.039791 -0.679808

28 6 0 2.276976 1.153192 0.376232

29 1 0 0.354088 2.047906 0.670284

30 6 0 2.999660 0.000047 0.001978

31 1 0 2.810999 -2.043979 -0.678089

32 1 0 2.813689 2.044402 0.681717

33 7 0 4.403421 -0.001982 0.005358

34 6 0 5.136019 1.195848 -0.256831

35 6 0 6.206533 1.562027 0.571472

36 6 0 4.807291 2.005004 -1.354639

37 6 0 6.936216 2.718555 0.300998

38 1 0 6.461522 0.936649 1.421294

39 6 0 5.531496 3.168807 -1.607483

40 1 0 3.987338 1.716730 -2.005201

41 6 0 6.600751 3.529928 -0.784873

42 1 0 7.763526 2.991215 0.950604

43 1 0 5.266787 3.786830 -2.461167

44 1 0 7.167835 4.433528 -0.989067

45 6 0 5.131265 -1.202123 0.270352

46 6 0 6.203893 -1.571531 -0.553760

47 6 0 4.795554 -2.010392 1.366688

48 6 0 6.928844 -2.730419 -0.280618

49 1 0 6.464297 -0.946840 -1.402443

50 6 0 5.515079 -3.176522 1.622170

51 1 0 3.973900 -1.719649 2.014010

52 6 0 6.586457 -3.540891 0.803747


S 42

53 1 0 7.757867 -3.005585 -0.926976

54 1 0 5.245004 -3.793890 2.474641

55 1 0 7.149785 -4.446356 1.010070

---------------------------------------------------------------------

Total Energy = -1506.0416803 HF

DFT data for meso-arylethynyl BODIPY 2c


---------------------------------------------------------------------



---------------------------------------------------------------------

1 6 0 -2.699110 -2.549335 -0.248511

2 1 0 -1.659089 -2.842054 -0.288743

3 6 0 -3.820621 -3.365202 -0.336889

4 1 0 -3.846034 -4.439374 -0.457964

5 6 0 -4.944349 -2.518784 -0.245727

6 1 0 -5.996073 -2.770503 -0.272128

7 7 0 -4.555533 -1.240697 -0.108267

8 5 0 -5.501829 -0.006614 0.106262

9 6 0 -3.819996 3.380703 0.101241

10 6 0 -2.698653 2.560070 0.081984

11 1 0 -1.658584 2.855371 0.081383

12 6 0 -3.165734 1.223314 0.048809

13 6 0 -2.463135 0.001111 -0.018031

14 6 0 -3.165924 -1.219565 -0.107331


S 43

15 7 0 -4.555344 1.244679 0.051194

16 9 0 -6.436023 0.058199 -0.908739

17 6 0 -4.943888 2.529835 0.081971

18 1 0 -5.995551 2.783074 0.089656

19 9 0 -6.102987 -0.085784 1.348870

20 1 0 -3.845210 4.461487 0.121576

21 6 0 -1.050207 0.001009 -0.017200

22 6 0 0.168387 0.000699 -0.012385

23 6 0 1.587791 0.000304 -0.006867

24 6 0 2.309054 1.211840 0.014933

25 6 0 2.308494 -1.211660 -0.022752

26 6 0 3.696903 1.205410 0.020180

27 1 0 1.767121 2.152146 0.037353

28 6 0 3.696343 -1.206027 -0.016753

29 1 0 1.766197 -2.151663 -0.048877

30 6 0 4.422475 -0.000521 0.004643

31 1 0 4.231582 2.149466 0.064584

32 1 0 4.230807 -2.150409 -0.056539

33 6 0 5.905180 -0.000938 0.010894

34 6 0 6.629831 0.973535 -0.697137

35 6 0 6.623199 -0.975780 0.725156

36 6 0 8.023444 0.972325 -0.692015

37 1 0 6.096434 1.719415 -1.279630

38 6 0 8.016800 -0.975238 0.732121

39 1 0 6.084419 -1.721342 1.303077

40 6 0 8.722948 -0.001626 0.023104


S 44

41 1 0 8.563740 1.729022 -1.254463

42 1 0 8.551827 -1.732152 1.299289

43 1 0 9.809417 -0.001868 0.027836

---------------------------------------------------------------------

Total Energy= -1219.6478668 HF

DFT data for meso-arylethynyl BODIPY 2d


---------------------------------------------------------------------



---------------------------------------------------------------------

1 6 0 -2.121916 -2.597946 -0.070808

2 1 0 -1.114658 -2.990482 -0.087768

3 6 0 -3.316376 -3.307509 -0.099042

4 1 0 -3.444654 -4.380343 -0.140477

5 6 0 -4.353985 -2.353524 -0.069308

6 1 0 -5.424987 -2.505457 -0.076169

7 7 0 -3.844708 -1.111611 -0.025749

8 5 0 -4.669868 0.219273 0.088762


S 45

9 6 0 -2.669109 3.423010 -0.104128

10 6 0 -1.631858 2.498690 -0.074556

11 1 0 -0.568224 2.691694 -0.092083

12 6 0 -2.225311 1.213453 -0.028205

13 6 0 -1.643000 -0.072080 -0.017509

14 6 0 -2.459384 -1.223036 -0.026381

15 7 0 -3.606380 1.368270 -0.027624

16 9 0 -5.578109 0.305976 -0.948045

17 6 0 -3.869530 2.684462 -0.073294

18 1 0 -4.891915 3.037801 -0.080705

19 9 0 -5.294728 0.280060 1.320528

20 1 0 -2.590485 4.500557 -0.147249

21 6 0 -0.236316 -0.206555 -0.015463

22 6 0 0.977354 -0.314805 -0.009397

23 6 0 2.390697 -0.453565 -0.001825

24 6 0 3.211833 0.669281 -0.002123

25 6 0 2.983436 -1.755729 0.006904

26 6 0 4.621059 0.546401 0.006080


S 46

27 1 0 2.765513 1.659596 -0.008411

28 6 0 4.347250 -1.897188 0.015006

29 1 0 2.335191 -2.626071 0.007424

30 6 0 5.475628 1.683309 0.006058

31 6 0 5.206454 -0.762973 0.014904

32 1 0 4.791402 -2.889412 0.021822

33 6 0 6.843390 1.533554 0.014427

34 1 0 5.028476 2.674255 -0.000555

35 6 0 6.619944 -0.881601 0.023376

36 6 0 7.420616 0.239606 0.023171

37 1 0 7.487225 2.408533 0.014421

38 1 0 7.062336 -1.874718 0.030126

39 1 0 8.502001 0.135221 0.029762

---------------------------------------------------------------------

Total Energy = -1142.2341676HF

DFT data for meso-arylethynyl BODIPY 2e


---------------------------------------------------------------------



S 47


---------------------------------------------------------------------

1 6 0 2.058509 2.696533 -0.074515

2 1 0 1.096740 3.188910 -0.090135

3 6 0 3.319303 3.280556 -0.113173

4 1 0 3.555662 4.333886 -0.162398

5 6 0 4.254795 2.226123 -0.083921

6 1 0 5.335205 2.268755 -0.097670

7 7 0 3.621089 1.042721 -0.030716

8 5 0 4.303930 -0.363521 0.107868

9 6 0 1.996310 -3.347885 -0.149356

10 6 0 1.056266 -2.324980 -0.102814

11 1 0 -0.020789 -2.410369 -0.121710

12 6 0 1.775547 -1.106407 -0.039181

13 6 0 1.325122 0.231754 -0.017144

14 6 0 2.254748 1.294630 -0.024820

15 7 0 3.133904 -1.398322 -0.044832

16 9 0 5.233227 -0.543240 -0.898426


S 48

17 6 0 3.264831 -2.733746 -0.110831

18 1 0 4.246127 -3.187733 -0.126424

19 9 0 4.876839 -0.485026 1.361120

20 1 0 1.810270 -4.410697 -0.209499

21 6 0 -0.059705 0.507855 -0.011444

22 6 0 -1.255465 0.745369 -0.004689

23 6 0 -2.765932 1.045394 0.003844

24 6 0 -3.677305 -0.046174 0.011484

25 6 0 -3.227473 2.338432 0.003377

26 6 0 -3.227505 -1.395172 0.012157

27 6 0 -5.071685 0.216198 0.018724

28 6 0 -4.619143 2.600909 0.010692

29 1 0 -2.525302 3.185074 -0.002501

30 6 0 -4.129029 -2.430443 0.019353

31 1 0 -2.144466 -1.589404 0.006571

32 6 0 -5.982982 -0.875025 0.026254

33 6 0 -5.520653 1.565549 0.018160

34 1 0 -4.964591 3.645218 0.009977


S 49

35 6 0 -5.520536 -2.168163 0.026442

36 1 0 -3.783596 -3.474792 0.019809

37 1 0 -7.062141 -0.660905 0.031627

38 1 0 -6.603639 1.760176 0.023777

39 1 0 -6.222787 -3.014748 0.032240

---------------------------------------------------------------------


DFT data for meso-arylethynyl BODIPY 2f


---------------------------------------------------------------------



---------------------------------------------------------------------

1 6 0 -2.348991 -2.685926 0.321721

2 1 0 -1.307306 -2.973245 0.357634

3 6 0 -3.465696 -3.507336 0.418492

4 1 0 -3.484797 -4.580580 0.548599

5 6 0 -4.594391 -2.669836 0.307102

6 1 0 -5.644713 -2.926831 0.337913


S 50

7 7 0 -4.212905 -1.392463 0.145869

8 5 0 -5.163370 -0.144276 0.094492

9 6 0 -3.508365 3.144483 -0.768879

10 6 0 -2.380843 2.353548 -0.582407

11 1 0 -1.343849 2.645097 -0.676481

12 6 0 -2.837812 1.048962 -0.272694

13 6 0 -2.127763 -0.149483 -0.043447

14 6 0 -2.823439 -1.362563 0.148116

15 7 0 -4.227507 1.060765 -0.273982

16 9 0 -6.123550 -0.316170 -0.882864

17 6 0 -4.625847 2.308798 -0.569211

18 1 0 -5.679447 2.547324 -0.625340

19 9 0 -5.731145 0.063893 1.337972

20 1 0 -3.541318 4.193919 -1.027203

21 6 0 -0.714705 -0.141744 -0.027783

22 6 0 0.504071 -0.146533 -0.005628

23 6 0 1.923610 -0.171857 0.005577

24 6 0 2.574229 -1.372448 -0.163019


S 51

25 6 0 2.690003 1.052841 0.178791

26 6 0 3.996109 -1.463735 -0.192359

27 1 0 1.992327 -2.280892 -0.289228

28 6 0 4.114562 0.995675 0.152252

29 6 0 2.045057 2.292346 0.381524

30 6 0 4.627628 -2.718049 -0.376384

31 6 0 4.785470 -0.284562 -0.040437

32 6 0 4.827562 2.205882 0.321222

33 1 0 0.960558 2.314714 0.417917

34 6 0 2.771511 3.455784 0.545198

35 6 0 6.002812 -2.820425 -0.411964

36 1 0 4.005474 -3.602317 -0.490331

37 6 0 6.191139 -0.424917 -0.082672

38 6 0 4.175909 3.410121 0.511620

39 1 0 5.911593 2.199410 0.305710

40 1 0 2.258827 4.400568 0.701812

41 6 0 6.787211 -1.660695 -0.263726

42 1 0 6.478513 -3.786512 -0.553758


S 52

43 1 0 6.827713 0.445757 0.027430

44 1 0 4.753381 4.321443 0.639178

45 1 0 7.870849 -1.734079 -0.291517

---------------------------------------------------------------------


DFT data for meso-arylethynyl BODIPY 2g


---------------------------------------------------------------------



---------------------------------------------------------------------

1 6 0 -2.347029 -2.349957 -0.356413

2 1 0 -1.270948 -2.404794 -0.445485

3 6 0 -3.261808 -3.393274 -0.442051

4 1 0 -3.051709 -4.442159 -0.599796

5 6 0 -4.541109 -2.821495 -0.294475

6 1 0 -5.511385 -3.299555 -0.302232

7 7 0 -4.440566 -1.492594 -0.126204

8 5 0 -5.629928 -0.506943 0.150286


S 53

9 6 0 -4.757986 3.171344 0.135598

10 6 0 -3.481114 2.624247 0.086919

11 1 0 -2.534730 3.146723 0.070314

12 6 0 -3.635690 1.217216 0.045308

13 6 0 -2.676505 0.184923 -0.054093

14 6 0 -3.091434 -1.161751 -0.158903

15 7 0 -4.993967 0.925296 0.073447

16 9 0 -6.600680 -0.650269 -0.821705

17 6 0 -5.661538 2.089686 0.127276

18 1 0 -6.742754 2.098931 0.159325

19 9 0 -6.139552 -0.727310 1.416941

20 1 0 -5.025040 4.218626 0.168134

21 6 0 -1.302494 0.506415 -0.069487

22 6 0 -0.117300 0.797200 -0.070116

23 6 0 1.249214 1.168251 -0.077977

24 6 0 2.283115 0.190577 0.001294

25 6 0 1.587831 2.535656 -0.170905

26 6 0 3.643469 0.621835 -0.024603


S 54

27 6 0 2.009020 -1.211673 0.112330

28 6 0 2.908842 2.946882 -0.194314

29 1 0 0.787893 3.266908 -0.228556

30 6 0 4.697133 -0.338510 0.049672

31 6 0 3.958808 2.012132 -0.124380

32 6 0 3.016314 -2.127174 0.183638

33 1 0 0.972944 -1.532041 0.147201

34 1 0 3.145229 4.004990 -0.269016

35 6 0 4.393848 -1.729025 0.152762

36 6 0 6.059835 0.088332 0.022302

37 6 0 5.335608 2.411541 -0.149101

38 1 0 2.785819 -3.186234 0.268570

39 6 0 5.446859 -2.656398 0.223759

40 6 0 7.079012 -0.875200 0.095632

41 6 0 6.339856 1.492629 -0.079490

42 1 0 5.563677 3.471592 -0.225594

43 6 0 6.773495 -2.231623 0.194824

44 1 0 5.214525 -3.715448 0.302722


S 55

45 1 0 8.116281 -0.550366 0.074296

46 1 0 7.378762 1.812482 -0.099735

47 1 0 7.575403 -2.962352 0.250574

---------------------------------------------------------------------


DFT data for meso-arylethynyl BODIPY 2h


---------------------------------------------------------------------



---------------------------------------------------------------------

1 6 0 -2.004628 -2.420783 -0.810645

2 1 0 -0.964612 -2.689306 -0.935439

3 6 0 -3.124070 -3.202512 -1.071836

4 1 0 -3.146101 -4.221693 -1.432334

5 6 0 -4.249908 -2.403614 -0.788480

6 1 0 -5.300932 -2.646541 -0.868599

7 7 0 -3.864384 -1.186586 -0.370467

8 5 0 -4.815163 -0.027555 0.093638


S 56

9 6 0 -3.148561 3.282050 0.840548

10 6 0 -2.023216 2.488649 0.649735

11 1 0 -0.985216 2.777211 0.742055

12 6 0 -2.483825 1.193455 0.308595

13 6 0 -1.775712 0.016100 -0.018366

14 6 0 -2.475236 -1.159420 -0.370462

15 7 0 -3.873270 1.210753 0.303000

16 9 0 -5.747910 0.243189 -0.888322

17 6 0 -4.268110 2.455191 0.619042

18 1 0 -5.321012 2.696312 0.676863

19 9 0 -5.418873 -0.363756 1.291413

20 1 0 -3.178410 4.329692 1.106484

21 6 0 -0.363957 0.017880 -0.013865

22 6 0 0.856473 0.013063 -0.006700

23 6 0 2.271904 0.002711 0.002090

24 6 0 2.966020 -1.223881 0.213777

25 6 0 2.988659 1.217585 -0.200659

26 6 0 2.291525 -2.459568 0.436491


S 57

27 6 0 4.406856 -1.223001 0.216986

28 6 0 4.429191 1.193275 -0.185096

29 6 0 2.337456 2.463952 -0.432399

30 6 0 2.994022 -3.621951 0.634716

31 1 0 1.206715 -2.464768 0.457567

32 6 0 5.101325 -2.454443 0.426708

33 6 0 5.095612 -0.020373 0.020436

34 6 0 5.146224 2.413247 -0.385782

35 1 0 1.253229 2.486226 -0.467528

36 6 0 3.061097 3.614748 -0.621718

37 6 0 4.416758 -3.623553 0.627892

38 1 0 2.459612 -4.552805 0.802891

39 1 0 6.188388 -2.440382 0.425179

40 1 0 6.183603 -0.029228 0.027623

41 6 0 4.483469 3.593262 -0.596105

42 1 0 6.232799 2.381604 -0.369941

43 1 0 2.544151 4.554149 -0.796866

44 1 0 4.954122 -4.554033 0.786968


S 58

45 1 0 5.037905 4.514869 -0.748073

---------------------------------------------------------------------


(1) U. Resch-Genger, and P. C. DeRose, Pure Appl. Chem., 2010, 82, 2315–2335.

(2) (a) A. D. Becke, J. Chem. Phys., 1993, 98, 5648-5652; (b) C. T. Lee, W. T. Yang and R. G. Parr,

Phys. Rev. B, 1988, 37, 785-789; (c) P. J. Hay and W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283; (d) M.

M. Francl, W. J. Pietro, W. J. Hehre, J. S. Binkley, M.S. Gordon, D. J. Defrees and J. A. Pople, J. Chem.

Phys. 1982, 77, 3654-3665.


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