supporting information1 supporting information novel germanetellones: xyge=te (x, y=h, f, cl, br, i...

1

SUPPORTING INFORMATION

Novel Germanetellones: XYGe=Te (X, Y=H, F, Cl, Br, I and CN) – Structures and

Energetics. Comparison with the First Synthetic Successes

Naziah B. Jaufeerally,† Hassan H. Abdallah,‡ Ponnadurai Ramasami†* and

Henry F. Schaefer III₰*

†Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, Mauritius. ‡Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, Johor, Malaysia. ₰Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States. *To whom correspondence should be addressed: [email protected] (P.R.); [email protected] (H.F.S.).

Index Figure SI 1 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of Cl2Ge=Te,

3A" state of Cl2Ge=Te, 2B" state of the Cl2Ge=Te+ cation, and 2B′ state of the Cl2Ge=Te-

anion. Figure SI 2 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of Br2Ge=Te,

3A" state of Br2Ge=Te, 2B" state of the Br2Ge=Te+ cation, and 2B′ state of the Br2Ge=Te-

anion. Figure SI 3 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of I2Ge=Te,

3A" state of I2Ge=Te, 2B" state of the I2Ge=Te+ cation, and 2B′ state of the I2Ge=Te-anion. Figure SI 4 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of HClGe=Te,

3A" state of HClGe=Te, 2B" state of the HClGe=Te+ cation, and 2B′ state of the HClGe=Te-

anion. Figure SI 5 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of HBrGe=Te,

3A" state of HBrGe=Te, 2B" state of the HBrGe=Te+ cation, and 2B′ state of the HBrGe=Te-

anion. Figure SI 6 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of HIGe=Te,

3A" state of HIGe=Te, 2B" state of the HIGe=Te+ cation, and 2B′ state of the HIGe=Te-

anion. Figure SI 7 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of FClGe=Te,

3A" state of FClGe=Te, 2B" state of the FClGe=Te+ cation, and 2B′ state of the FClGe=Te-

anion. Figure SI 8 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of FBrGe=Te,

3A" state of FBrGe=Te, 2B" state of the FBrGe=Te+ cation, and 2B′ state of the FBrGe=Te-

anion. Figure SI 9 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of FIGe=Te,

3A" state of FIGe=Te, 2B" state of the FIGe=Te+ cation, and 2B′ state of the FIGe=Te- anion.

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

2

Index

Figure SI 10 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of ClBrGe=Te, 3A" state of ClBrGe=Te, 2B" state of the ClBrGe=Te+ cation, and 2B′ state of the ClBrGe=Te-

anion. Figure SI 11 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of ClIGe=Te,

3A" state of ClIGe=Te, 2B" state of the ClIGe=Te+ cation, and 2B′ state of the ClIGe=Te-

anion. Figure SI 12 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of

Cl(NC)Ge=Te, 3A" state of Cl(NC)Ge=Te, 2B" state of the Cl(NC)Ge=Te +cation, and 2B′ state of the Cl(NC)Ge=Te- anion.

Figure SI 13 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of BrIGe=Te, 3A" state of BrIGe=Te, 2B" state of the BrIGe=Te+ cation, and 2B′ state of the BrIGe=Te-

anion. Figure SI 14 Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of

Br(NC)Ge=Te, 3A" state of Br(NC)Ge=Te, 2B" state of the Br(NC)Ge=Te+ cation, and 2B′ state of the (NC)Ge=Te- anion.

Figure SI 15 Equilibrium geometry (bond lengths in Å, bond angles in °) for the 1A′ state of Tbt(Tip)Ge=Te (all the H atoms are omitted for clarity) optimized using the BP86/TZVP method.

Figure SI 16 Equilibrium geometry (bond lengths in Å, bond angles in °) for the 1A′ state of Tbt(Dis)Ge=Te (all the H atoms are omitted for clarity) optimized using the BP86/TZVP method.

Table SI 1 Structural parameters for germanium containing heavy ketones. Table SI 2 Vertical Electron Affinities (VEA) in eV (kcal mol-1 in parentheses) for the H(2-n)X(n)Ge=Te

(X=H, F, Cl and Br; n=0, 1, 2) molecules. Table SI 3 Vertical Detachment Energies (VDE) in eV (kcal mol-1 in parentheses) for the H(2-

n)X(n)Ge=Te (X=H, F, Cl and Br; n=0, 1, 2) molecules. Table SI 4 HOMO-LUMO gap for the Singlet Ground States of all the Scrutinized Germanetellones.

Computed total energy and cartesian coordinates of 1A′ state of Tbt(Tip)Ge=Te and Tbt(Dis)Ge=Te

Complete citation for reference 44.


Cl2Ge=Te (1A′,Cs) Cl2Ge=Te (3A",Cs)

Cl2Ge=Te+ (2B", Cs) Cl2Ge=Te– (2A", Cs)

Figure SI 1: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of Cl2Ge=Te, 3A" state of Cl2Ge=Te, 2B" state of the Cl2Ge=Te+ cation, and 2B′ state of the Cl2Ge=Te– anion.

2.339 2.365 2.398 2.344

2.172 2.225 2.263 2.191

2.590 2.654 2.698 2.616

109.0 108.0 107.3 108.5

2.132 2.167 2.199 2.139

128.1 128.2 128.1 128.2

122.4 122.7 122.5 122.8

2.447 2.474 2.498 2.454

2.262 2.333 2.377 2.292

115.4 112.8 113.0 113.1

2.462 2.550 2.584 2.516

2.071 2.103 2.131 2.078

MP2 103.9 B3LYP 103.7 BLYP 103.8 BHLYP 103.6

106.4 106.2 106.7 105.9


98.7 98.8 99.6 98.3


1

Br2Ge=Te (1A′,Cs) Br2Ge=Te (3A",Cs)

Br2Ge=Te+ (2B", Cs) Br2Ge=Te– (2A", Cs)

Figure SI 2: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of Br2Ge=Te, 3A" state of Br2Ge=Te, 2B" state of the Br2Ge=Te+ cation, and 2B′ state of the Br2Ge=Te– anion.

2.343 2.370 2.394 2.349

2.338 2.386 2.429 2.350

2.583 2.637 2.673 2.604

108.7 107.9 107.1 108.5

2.294 2.324 2.357 2.295

127.5 127.4 127.3 127.4

121.5 121.5 121.4 121.7

2.451 2.477 2.500 2.258

2.444 2.506 2.554 2.464

115.4 113.4 114.0 113.3

2.454 2.535 2.564 2.507

2.227 2.255 2.285 2.229


108.0 108.4 109.1 107.9

117.1 116.9 117.2 116.6

99.5 100.3 101.2 99.7


2

I2Ge=Te (1A′,Cs) I2Ge=Te (3A",Cs)

I2Ge=Te+ (2B", Cs) I2Ge=Te– (2A", Cs)

Figure SI 3: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of I2Ge=Te, 3A" state of I2Ge=Te, 2B" state of the I2Ge=Te+ cation, and 2B′ state of the I2Ge=Te– anion.

2.351 2.376 2.401 2.351

2.545 2.605 2.652 2.567

2.574 2.614 2.639 2.588 108.8

107.6 106.5 108.5

2.498 2.554 2.566 2.505

126.2 126.3 126.3 126.3

120.2 120.2 120.2 120.4

2.457 2.479 2.496 2.462

2.663 2.742 2.794 2.698

115.5 114.2 115.1 113.6

2.447 2.513 2.537 2.492

2.427 2.459 2.498 2.435


110.4 111.1 111.8 110.4

119.6 119.5 119.7 119.2

101.7 102.4 103.4 101.6


3

HClGe=Te (1A′,Cs) HClGe=Te (3A",Cs)

HClGe=Te+ (2B", Cs) HClGe=Te– (2A", Cs)

Figure SI 4: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of HClGe=Te, 3A" state of HClGe=Te, 2B" state of the HClGe=Te+ cation, and 2B′ state of the HClGe=Te– anion.

1.519 1.537 1.552 1.523

2.177 2.229 2.268 2.197

2.565 2.607 2.645 2.578

108.5 105.8 103.6 107.0

2.149 2.186 2.218 2.159

125.2 125.2 125.5 125.1

119.5 118.6 118.3 118.8

125.3 127.1 127.5 126.7

2.289 2.368 2.418 2.324

115.7 114.1 114.1 114.5

2.466 2.531 2.569 2.497

2.075 2.106 2.131 2.083


105.2 103.2 102.2 104.2

115.2 114.3 114.2 114.5

97.1 95.5 95.3 96.0

2.341 2.359 2.382 2.339

109.3 107.8 106.3 109.4

1.539 1.571 1.593 1.550

1.555 1.588 1.609 1.567

114.2 108.6 106.3 111.5

1.511 1.530 1.544 1.516

2.435 2.457 2.481 2.438

130.9 131.6 131.6 131.4


4

Figure SI 5: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of HBrGe=Te, 3A" state of HBrGe=Te, 2B" state of the HBrGe=Te+ cation, and 2B′ state of the HBrGe=Te– anion.

HBrGe=Te (1A′,Cs) HBrGe=Te (3A",Cs)

HBrGe=Te+ (2B", Cs) HBrGe=Te– (2A", Cs)

2.342 2.362 2.385 2.342

2.339 2.384 2.432 2.350

2.561 2.602 2.634 2.575

108.3 105.8 101.3 107.6

2.308 2.336 2.369 2.308

125.5 126.0 126.3 125.8

120.0 119.7 119.3 120.0

123.9 124.7 125.3 124.4

2.473 2.543 2.597 2.496

116.0 114.8 115.1 115.1

2.462 2.529 2.564 2.496

2.225 2.249 2.277 2.227

105.4 103.7 102.5 104.7

116.1 115.5 115.4 115.6

96.5 95.3 95.2 95.8

130.3 130.2 130.1 130.1

1.540 1.571 1.593 1.550

109.2 107.4 106.3 108.8

1.520 1.539 1.553 1.525

1.555 1.587 1.608 1.566

113.9 108.1 106.0 111.0

1.513 1.532 1.546 1.518

2.436 2.459 2.482 2.440


5

HIGe=Te (1A′,Cs) HIGe=Te (3A",Cs)

HIGe=Te+ (2B", Cs) HIGe=Te– (2A", Cs)

Figure SI 6: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of HIGe=Te, 3A" state of HIGe=Te, 2B" state of the HIGe=Te+ cation, and 2B′ state of the HIGe=Te– anion.

1.522 1.540 1.555 1.526

2.537 2.594 2.659 2.558

2.559 2.594 2.618 2.570

109.5 105.6 96.5 108.7

2.502 2.536 2.568 2.509

126.4 126.9 127.3 126.5

121.8 121.2 120.1 121.7

1.514 1.533 1.547 1.519

2.685 2.779 2.838 2.729

116.7 115.6 116.2 115.7

2.462 2.526 2.560 2.494

2.414 2.442 2.470 2.421


106.0 104.3 102.3 105.4

117.8 117.1 117.0 117.1

96.4 95.2 95.0 95.5

128.3 128.3 128.1 128.3

2.348 2.367 2.390 2.346

1.555 1.587 1.607 1.566

113.2 107.5 105.5 110.2

120.4 121.7 122.9 121.3

2.440 2.461 2.481 2.443

108.2 106.8 106.1 107.7

1.540 1.571 1.594 1.550


6

FClGe=Te (1A′,Cs) FClGe=Te (3A",Cs)

FClGe=Te+ (2B", Cs) FClGe=Te– (2A", Cs)

Figure SI 7: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of FClGe=Te, 3A" state of FClGe=Te, 2B" state of the FClGe=Te+ cation, and 2B′ state of the FClGe=Te– anion.

2.335 2.361 2.385 2.341

2.167 2.222 2.262 2.187

2.605 2.680 2.729 2.637

110.3 109.6 108.3 110.2

2.120 2.156 2.187 2.128

132.0 132.0 132.1 132.0

129.3 129.5 129.4 129.5

118.2 118.4 118.2 118.6

2.263 2.342 2.390 2.298

116.6 114.4 114.6 114.7

2.471 2.564 2.605 2.527

2.058 2.089 2.117 2.065


104.2 103.8 104.2 103.5

112.6 112.1 112.4 111.8

96.6 96.7 97.2 96.3

1.741 1.745 1.773 1.718

107.1 105.8 105.9 106.1

1.763 1.773 1.803 1.744

127.1 127.0 126.8 127.1

1.704 1.709 1.734 1.685 2.445

2.473 2.498 2.452

114.6 111.3 110.9 112.0

1.807 1.819 1.851 1.786


7

FBrGe=Te (1A′,Cs) FBrGe=Te (3A",Cs)

FBrGe=Te+ (2B", Cs) FBrGe=Te– (2A", Cs)

Figure SI 8: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of FBrGe=Te, 3A" state of FBrGe=Te, 2B" state of the FBrGe=Te+ cation, and 2B′ state of the FBrGe=Te– anion.

1.744 1.749 1.776 1.722

2.332 2.381 2.428 2.345

2.601 2.670 2.712 2.630

110.1 110.1 106.8 111.1

2.278 2.306 2.339 2.278

132.3 132.8 132.9 132.6

130.0 130.8 130.7 130.8

2.448 2.475 2.500 2.455

2.450 2.520 2.573 2.474

117.0 115.3 115.8 115.5

2.467 2.557 2.594 2.522

2.208 2.234 2.264 2.209


105.2 104.8 105.2 104.4

113.5 113.0 113.2 112.7

96.9 97.1 97.7 96.6

126.3 125.7 125.5 126.0

2.337 2.364 2.388 2.344

106.9 105.4 106.7 105.4

1.764 1.775 1.805 1.746

116.6 116.2 116.1 116.5

1.708 1.714 1.739 1.689

114.3 111.0 110.7 111.7

1.806 1.819 1.851 1.786


8

FIGe=Te (1A′,Cs) FIGe=Te (3A",Cs)

FIGe=Te+ (2B", Cs) FIGe=Te– (2A", Cs)

Figure SI 9: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of FIGe=Te, 3A" state of FIGe=Te, 2B" state of the FIGe=Te+ cation, and 2B′ state of the FIGe=Te– anion.

124.8 124.3 124.1 124.6

2.473 2.507 2.539 2.480

1.750 1.754 1.782 1.727

131.6 132.3 131.8 132.5

2.452 2.477 2.499 2.458

2.669 2.763 2.821 2.713

117.9 116.4 117.2 116.3

113.8 110.7 110.6 111.2

2.399 2.429 2.458 2.406


114.4 113.8 113.8 113.6

97.2 97.3 97.9 96.8

2.341 2.367 2.390 2.346

133.2 133.7 133.9 133.5

105.9 105.1 109.5 104.4

2.595 2.655 2.681 2.619

1.768 1.778 1.807 1.749

2.536 2.599 2.664 2.561

111.5 110.4 99.8 112.6

106.0 105.7 105.7 105.3

1.715 1.720 1.746 1.695

114.0 113.9 114.4 114.0

1.808 1.819 1.850 1.786 2.462

2.546 2.580 2.514


9

ClBrGe=Te (1A′,Cs) ClBrGe=Te (3A",Cs)

ClBrGe=Te+ (2B", Cs) ClBrGe=Te– (2A", Cs)

Figure SI 10: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of ClBrGe=Te, 3A" state of ClBrGe=Te, 2B" state of the ClBrGe=Te+ cation, and 2B′ state of the ClBrGe=Te– anion.

127.3 126.8 126.7 126.9

2.336 2.383 2.428 2.347

109.0 107.6 108.4 107.8

108.7 108.3 105.7 109.2 2.290

2.318 2.351 2.289

128.2 128.8 128.8 128.7

123.0 123.9 123.7 124.0

120.9 120.3 120.3 120.5

2.447 2.508 2.557 2.465

115.7 113.6 114.2 113.7

115.1 112.5 112.8 112.7

2.222 2.248 2.278 2.223


107.3 107.3 107.9 106.9

116.2 115.8 116.1 115.5

99.1 99.6 100.4 99.0

2.135 2.173 2.205 2.144 2.341

2.368 2.392 2.347

2.449 2.476 2.499 2.456

2.173 2.228 2.265 2.194

2.587 2.646 2.684 2.610

2.076 2.110 2.138 2.085

2.260 2.332 2.375 2.291 2.458

2.542 2.574 2.512


10

ClIGe=Te (1A′,Cs) ClIGe=Te (3A",Cs)

ClIGe=Te+ (2B", Cs) ClIGe=Te– (2A", Cs)

Figure SI 11: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of ClIGe=Te, 3A" state of ClIGe=Te, 2B" state of the ClIGe=Te+ cation, and 2B′ state of the ClIGe=Te– anion.

2.345 2.371 2.395 2.349

110.0 108.3 99.0 110.5

2.582 2.633 2.657 2.601

107.8 107.2 111.5 106.7

2.486 2.519 2.551 2.492

128.9 129.4 129.5 129.4

124.6 125.3 124.5 125.6

2.453 2.477 2.498 2.459

2.665 2.748 2.804 2.702

116.5 114.7 115.5 114.4

114.5 112.2 112.6 112.3

2.412 2.443 2.473 2.419


108.4 108.6 108.9 108.0

117.4 117.0 117.1 116.7

99.9 100.4 101.2 99.7

2.539 2.600 2.663 2.577

2.178 2.231 2.267 2.198

125.5 125.1 125.0 125.3

2.143 2.181 2.213 2.152

2.085 2.119 2.147 2.094

118.0 117.7 118.3 117.7

2.454 2.531 2.560 2.504

2.263 2.330 2.372 2.291


11

Cl(NC)Ge=Te (1A′,Cs) Cl(NC)Ge=Te (3A",Cs)

Cl(NC)Ge=Te+ (2B", Cs) Cl(NC)Ge=Te– (2A", Cs)

Figure SI 12: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of Cl(NC)Ge=Te, 3A" state of Cl(NC)Ge=Te, 2B" state of the Cl(NC)Ge=Te+ cation, and 2B′ state of the Cl(NC)Ge=Te– anion.

129.6 129.4 129.4 129.5

1.971 1.969 1.994 1.949

2.633 2.621 2.668 2.584

104.4 104.4 103.2 106.0

1.911 1.924 1.939 1.912

127.2 127.4 127.3 127.4

121.3 122.4 122.6 122.2

124.1 123.6 123.3 124.0

2.007 2.018 2.039 2.019

109.5 105.9 105.5 97.7

2.460 2.556 2.588 2.626

1.873 1.886 1.904 1.873


103.7 103.7 103.5 104.0

114.7 114.0 114.2 113.8

96.0 96.3 96.8 94.8

2.224 2.215 2.255 2.180

109.0 107.0 110.1

1.174 1.171 1.186 1.155

2.130 2.164 2.197 2.136 2.334

2.354 2.379 2.333

1.194 1.170 1.184 1.154

1.183 1.174 1.188 1.159

114.7 112.2 112.8 105.3

2.267 2.336 2.382 2.324

1.196 1.170 1.185 1.154

2.067 2.096 2.124 2.072

2.435 2.459 2.484 2.439


12

BrIGe=Te (1A′,Cs) BrIGe=Te (3A",Cs)

BrIGe=Te+ (2B", Cs) BrIGe=Te– (2A", Cs)

Figure SI 13: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of BrIGe=Te, 3A" state of BrIGe=Te, 2B" state of the BrIGe=Te+ cation, and 2B′ state of the BrIGe=Te– anion.

2.347 2.373 2.398 2.352

2.540 2.602 2.685 2.579

2.578 2.625 2.648 2.596

110.1 108.4 98.5 109.8 2.508

2.525 2.578 2.497

128.0 128.0 128.0 128.0

118.7 118.9 119.6 118.9

2.454 2.479 2.498 2.460

2.661 2.759 2.800 2.714

116.2 114.4 115.3 114.0

2.451 2.525 2.550 2.501

2.435 2.449 2.502 2.426


109.0 109.7 110.1 109.1

118.1 118.2 118.0 117.8

100.4 101.3 102.3 100.6

125.9 125.7 125.7 125.8

2.302 2.332 2.366 2.303

2.343 2.389 2.428 2.354

107.4 107.5 112.2 107.3

2.236 2.264 2.295 2.238

123.2 123.0 122.1 123.3

114.7 113.0 113.8 112.8

2.447 2.505 2.550 2.463


13

Br(NC)Ge=Te (1A′,Cs) Br(NC)Ge=Te (3A",Cs)

Br(NC)Ge=Te+ (2B", Cs) Br(NC)Ge=Te– (2A", Cs)

Figure SI 14: Equilibrium geometries (bond lengths in Å, bond angles in °) for the 1A′ state of Br(NC)Ge=Te, 3A" state of Br(NC)Ge=Te, 2B" state of the Br(NC)Ge=Te+ cation, and 2B′ state of the Br(NC)Ge=Te– anion.

129.9 130.2 130.3 130.2

1.982 1.969 1.994 1.949

2.59022.616 2.658 2.581

104.0 104.0 103.7 105.4 1.912

1.926 1.941 1.915

126.3 126.0 125.8 126.1

119.7 120.0 120.3 120.0

2.438 2.462 2.487 2.442

2.001 2.016 2.037 2.017

106.5 105.5 105.3 97.4

2.478 2.554 2.583 2.625

1.876 1.890 1.907 1.877


107.2 109.5 105.5 111.0

115.4 114.9 115.1 114.7

95.9 96.5 97.1 94.9

1.195 1.170 1.184 1.154

2.287 2.313 2.348 2.284 2.337

2.358 2.383 2.336

104.2 104.4 104.1 104.7

2.393 2.371 2.418 2.334

1.178 1.171 1.186 1.155

113.0 112.9 113.8 105.6

2.455 2.507 2.557 2.496

1.189 1.174 1.188 1.159

124.9 125.0 124.6 125.3

2.216 2.240 2.271 2.216

1.197 1.171 1.185 1.154


14

Figure SI 15: Equilibrium geometry (bond lengths in Å, bond angles in °) for the 1A′ state of Tbt(Tip)Ge=Te (all the H atoms are omitted for clarity) optimized using the BP86/TZVP method.

126.8

2.436

114.2

118.5 Ge Te


15

Figure SI 16: Equilibrium geometry (bond lengths in Å, bond angles in °) for the 1A′ state of Tbt(Dis)Ge=Te (all the H atoms are omitted for clarity) optimized using the BP86/TZVP method.

Te Ge 2.433

118.1

116.1

125.7


16

Table SI 1: Structural parameters for germanium containing heavy ketones.

a=ref 36, b=ref 30 c=ref 34, d=ref 12, e=ref 38, f=ref 18, g=ref 11, h=ref 13, i=ref 37, j=ref 41

r(Ge=E) r(Ge–X) H2Ge=O 1.644a 1.546a F2Ge=O 1.630a 1.726a Cl2Ge=O 1.634a 2.142a Br2Ge=O 1.638a 2.300a (Eind)2Ge=O 1.676b

H2Ge=S 2.051c

2.041d

2.051e

1.518c

1.544d 1.518e

F2Ge=S 2.021d 1.730d Cl2Ge=S 2.029d 2.150d Br2Ge=S 2.034d 2.308d Tbt(Tip)Ge=S 2.049f

H2Ge=Se 2.171g

2.160h 1.533g

1.527h F2Ge=Se 2.143g 1.753g Cl2Ge=Se 2.153g 2.129g Br2Ge=Se 2.158g 2.289g Tbt(Tip)Ge=Se 2.180i Tbt(Dis)Ge=Se 2.173i Tbt(Tip)Ge=Te 2.398j Tbt(Dis)Ge=Te 2.384j


17

Table SI 2: Vertical Electron Affinities (VEA) in eV (kcal mol-1 in parentheses) for the XYGe=Te (X, Y=H, F, Cl,Br , I and CN) molecules.

MP2 B3LYP BLYP BHLYP

H2Ge=Te 0.80 (18.47) 1.22 (28.11) 1.03 (23.87) 1.14 (26.28)

F2Ge=Te 0.29 (6.68) 2.71 (62.59) 1.44 (33.17) 0.97 (22.33)

Cl2Ge=Te 0.33 (7.72) 1.62 (37.37) 1.70 (39.22) 1.20 (27.67)

Br2Ge=Te 0.64 (14.78) 1.82 (41.96) 1.87 (43.16) 1.44 (33.11)

I2Ge=Te 0.95 (21.89) 2.04 (47.66) 2.05 (47.33) 1.71 (39.47)

(NC)2Ge=Te 1.52 (35.23) 2.65 (61.18) 2.45 (56.43) 2.59 (59.68)

HFGe=Te 0.82 (18.87) 1.10 (25.36) 0.92 (21.29) 1.98 (45.57)

HClGe=Te 0.52 (12.05) 0.58 (13.46) 1.11 (25.65) 0.17 (3.92)

HBrGe=Te 0.42 (9.77) 0.75 (17.20) 1.15 (26.56) 0.35 (8.18)

HIGe=Te 1.04 (24.06) 1.43 (32.87) 1.22 (28.18) 1.37 (31.59)

H(NC)Ge=Te 1.63 (37.66) 1.96 (45.24) 1.77 (40.72) 1.89 (43.59)

FClGe=Te 0.26 (6.08) 1.46 (33.75) 1.54 (35.61) 1.05 (24.18)

FBrGe=Te 0.41 (9.50) 1.56 (36.00) 1.63 (37.54) 1.16 (26.78)

FIGe=Te 0.56 (12.91) 1.67 (38.52) 1.72 (39.56) 1.30 (29.97)

F(NC)Ge=Te 1.59 (36.69) 1.91 (43.98) 1.73 (39.79) 1.81 (41.81)

ClBrGe=Te 0.49 (11.38) 1.72 (39.77) 1.79 (41.30) 1.32 (30.52)

ClIGe=Te 0.67 (15.38) 1.85 (42.57) 1.89 (43.56) 1.48 (34.04)

Cl(NC)Ge=Te 1.70 (39.22) 2.04 (47.06) 1.85 (42.63) 1.96 (45.27)

BrIGe=Te 0.80 (18.47) 1.93 (44.60) 1.96 (45.31) 1.58 (36.42)

Br(NC)Ge=Te 1.75 (40.27) 2.06 (47.46) 1.86 (42.89) 1.99 (45.88)


18

Table SI 3: Vertical Detachment Energies (VDE) in eV (kcal mol-1 in parentheses) for the XYGe=Te (X, Y=H, F, Cl, Br , I and CN) molecules.

MP2 B3LYP BLYP BHLYP

H2Ge=Te 2.06 (47.49) 2.46 (56.65) 2.29 (52.80) 2.38 (54.79)

F2Ge=Te 3.33 (76.86) 3.67 (84.71) 3.51 (81.07) 3.61 (83.36)

Cl2Ge=Te 3.37 (77.70) 3.86 (89.06) 3.09 (71.35) 3.82 (88.02)

Br2Ge=Te 3.40 (78.39) 3.81 (87.82) 3.59 (82.85) 3.79 (87.48)

I2Ge=Te 3.31 (76.25) 3.73 (85.99) 3.50 (80.63) 4.01 (92.39)

(NC)2Ge=Te 4.16 (95.84) 4.25 (98.07) 4.84 (111.76) 4.53 (104.57)

HFGe=Te 2.63 (60.63) 2.73 (62.99) 2.78 (64.08) 2.34 (54.02)

HClGe=Te 2.76 (63.67) 3.20 (73.83) 3.02 (69.54) 3.13 (72.15)

HBrGe=Te 2.83 (65.20) 3.23 (74.53) 3.03 (69.95) 3.17 (73.09)

HIGe=Te 2.85 (65.63) 3.27 (75.32) 3.06 (70.49) 3.22 (74.14)

H(NC)Ge=Te 3.12 (71.88) 3.34 (77.13) 3.13 (72.23) 3.29 (75.90)

FClGe=Te 3.36 (77.40) 3.78 (87.21) 3.58 (82.56) 3.73 (85.96)

FBrGe=Te 3.38 (77.91) 3.76 (86.71) 3.62 (83.89) 3.72 (85.81)

FIGe=Te 3.33 (76.72) 3.72 (85.85) 3.51 (80.87) 3.69 (85.16)

F(NC)Ge=Te 3.63 (83.72) 3.94 (90.83) 3.71 (85.46) 3.90 (89.94)

ClBrGe=Te 3.39 (78.07) 3.83 (88.39) 3.61 (83.20) 3.80 (87.74)

ClIGe=Te 3.34 (77.02) 3.79 (87.45) 3.57 (82.23) 3.77 (87.03)

Cl(NC)Ge=Te 3.71 (85.58) 4.08 (94.15) 3.82 (88.01) 4.54 (104.77)

BrIGe=Te 3.35 (77.35) 3.77 (86.83) 3.53 (81.45) 3.58 (86.72)

Br(NC)Ge=Te 3.84 (88.56) 4.07 (93.76) 3.79 (87.29) 4.55 (104.83)


19

Table SI 4: HOMO-LUMO gap for the Singlet Ground States of all the Scrutinized Germanetellones.

HOMO (a.u.) LUMO (a.u.) ΔEH-L (eV)

H2Ge=Te -0.22 -0.12 2.88

F2Ge=Te -0.26 -0.12 3.73

Cl2Ge=Te -0.25 -0.13 3.36

Br2Ge=Te -0.24 -0.13 3.10

I2Ge=Te -0.24 -0.14 2.79

(NC)2Ge=Te -0.27 -0.16 2.79

HFGe=Te -0.24 -0.11 3.55

HClGe=Te -0.24 -0.12 3.33

HBrGe=Te -0.24 -0.12 3.26

HIGe=Te -0.24 -0.12 3.15

H(NC)Ge=Te -0.25 -0.14 2.85

FClGe=Te -0.25 -0.12 3.57

FBrGe=Te -0.25 -0.13 3.43

FIGe=Te -0.25 -0.13 3.27

F(NC)Ge=Te -0.27 -0.14 3.39

ClBrGe=Te -0.25 -0.13 3.22

ClIGe=Te -0.24 -0.13 3.05

Cl(NC)Ge=Te -0.26 -0.14 3.18

BrIGe=Te -0.24 -0.13 2.94

Br(NC)Ge=Te -0.26 -0.14 3.12


20

Tbt(Tip)Ge=Te

E(RBP86) =-5733.3018363 au

C -1.98785000 -1.39080700 -0.23338700 C -2.97033100 -0.55287600 0.34239300 C -2.62087600 0.80056400 0.52568500 C -1.35188000 1.33535500 0.20700800 C -0.33461700 0.42970900 -0.27067000 C -0.68176600 -0.93993300 -0.55146400 H -2.24376700 -2.43877700 -0.45179600 H -3.38262400 1.48902000 0.92752300 C -1.18156500 2.83377600 0.35547000 H -0.12239100 3.10803800 0.14548000 C 0.26342000 -1.91846300 -1.23713100 C -4.35529500 -1.03317300 0.73790100 H -4.88872200 -0.14572100 1.15830600 H 1.29400100 -1.48986800 -1.24056300 Ge 1.55795600 1.03164900 -0.43482500 Te 2.33689300 3.20978400 -1.19794500 C 2.22763800 -4.31668700 -0.72578500 H 2.38361200 -5.25128800 -0.14469200 H 2.35459100 -4.56690700 -1.79805600 H 3.02844500 -3.60431100 -0.43598700 C 0.46331800 -3.32919500 1.55389000 H 1.34218900 -2.72303400 1.85725600 H -0.45022600 -2.79249000 1.88040500 H 0.51187200 -4.29645400 2.09790600 C -0.77500300 -4.93600400 -0.79403400 H -1.81929200 -4.63663900 -0.57060500 H -0.72121500 -5.20280300 -1.86996100 H -0.56937900 -5.86190000 -0.21465900 C -1.95281300 -2.52115700 -3.45858500 H -2.12243900 -2.57346700 -4.55561100 H -2.21756600 -3.51049400 -3.03257700 H -2.65395300 -1.76936900 -3.04558400 C 0.92071200 -3.39197100 -3.99254200 H 0.70761800 -4.41692300 -3.62549400 H 0.68883700 -3.37607300 -5.07949200 H 2.00797200 -3.20559600 -3.88457900 C 0.22272600 -0.40271000 -3.97451100 H -0.35614700 0.42808300 -3.52233000 H 1.29819700 -0.13339400 -3.91144600 H -0.04379400 -0.45235900 -5.05220600 C -7.32155600 -1.23174400 -0.24600600 H -7.97430000 -1.35948600 -1.13638300 H -7.66303600 -1.95203300 0.52410800 H -7.49468700 -0.20699400 0.14632700 C -5.29699000 -3.26967900 -1.36636200 H -4.24695500 -3.50328800 -1.63666500 H -5.62925000 -4.00688500 -0.60596200


21

H -5.91619700 -3.42795500 -2.27530200 C -5.15733800 -0.27361900 -2.17369800 H -5.43374300 0.76215100 -1.88407900 H -4.08760300 -0.26223200 -2.46628300 H -5.75552800 -0.54201000 -3.07040600 C -6.11125200 -2.47324100 2.91202900 H -6.65270300 -1.51378300 3.04950700 H -6.71736400 -3.11420900 2.23876000 H -6.07183200 -2.97893000 3.90087400 C -3.33349900 -1.37251300 3.64147300 H -2.29139800 -1.17231600 3.31672900 H -3.78671800 -0.40306200 3.93847600 H -3.29037100 -2.01471600 4.54702200 C -3.58492400 -3.92264400 1.92902200 H -2.51304700 -3.85670200 1.65486000 H -3.65264000 -4.54114100 2.84999700 H -4.11424400 -4.46694700 1.12065900 C -1.55078900 5.59985300 -1.05471600 H -1.96626200 6.12654900 -1.94048500 H -1.90856900 6.13608100 -0.15124800 H -0.44477200 5.68866100 -1.09716200 C -3.98008100 3.68080900 -1.01131400 H -4.33354200 2.63129000 -1.07810800 H -4.41315500 4.13556500 -0.09877900 H -4.39500200 4.22433900 -1.88791100 C -1.57106000 3.01424800 -2.74640100 H -0.46793700 3.02015000 -2.86868900 H -1.92821400 1.96637200 -2.82611800 H -2.01846500 3.58865200 -3.58589700 Si -4.33983100 -2.21466900 2.26867700 Si -5.50532300 -1.48376500 -0.75259500 Si 0.51086800 -3.61201000 -0.32076500 Si -0.14049100 -2.06461700 -3.13586100 Si -2.08069500 3.77534800 -1.08698300 Si -1.47063400 3.57967000 2.12004400 C -3.19364200 4.34017900 2.40843100 H -3.24412800 4.72067900 3.45168400 H -3.40324400 5.19613800 1.73434200 H -4.01294500 3.60095100 2.28712500 C -0.17524600 4.94370200 2.38981600 H -0.27271600 5.76311900 1.64854300 H -0.28351100 5.38824600 3.40238100 H 0.85464400 4.53805300 2.30284100 C -1.23241000 2.25510000 3.45838300 H -1.96325400 1.42680600 3.36171300 H -0.21761500 1.81246900 3.40955400 H -1.35690700 2.70701300 4.46571900 C 3.00246500 -0.14788700 0.29849100 C 4.00662200 -0.70145600 -0.54610700 C 3.09480000 -0.31579400 1.71158600 C 5.03179700 -1.47613500 0.03918500 C 4.13691200 -1.10194400 2.24289000


22

C 5.11156900 -1.70466000 1.42422700 H 5.80727400 -1.91530600 -0.61043000 H 4.19889700 -1.23079800 3.33543900 C 2.17827900 0.44831900 2.66975400 H 1.25990200 0.72547200 2.09472300 C 6.23609300 -2.55344800 2.01415000 H 6.85172200 -2.90659400 1.15645300 C 4.06710600 -0.43470100 -2.05240600 H 3.07563200 -0.01657900 -2.35152700 C 2.86444200 1.76257900 3.10870800 H 3.79039000 1.54396600 3.68169600 H 3.14606500 2.38591100 2.23508300 H 2.19421800 2.36154800 3.76095900 C 1.71542400 -0.36422700 3.89297600 H 1.24196100 -1.32184400 3.59828500 H 2.56092500 -0.59444300 4.57515100 H 0.97609000 0.21453100 4.48400800 C 7.15864600 -1.72482500 2.93323700 H 6.61242900 -1.35135500 3.82556000 H 8.00856900 -2.34032800 3.29695200 H 7.57472700 -0.84431200 2.40199900 C 5.69528800 -3.80296100 2.74020600 H 5.07934900 -3.52479700 3.62188600 H 5.06190700 -4.41877900 2.06919100 H 6.52945500 -4.43925900 3.10459900 C 5.12745100 0.64098800 -2.37221800 H 5.14484300 0.86102500 -3.46087000 H 4.91506900 1.58685800 -1.83399100 H 6.14007900 0.29065000 -2.07855900 C 4.31406300 -1.69996800 -2.89603100 H 4.20623500 -1.47110700 -3.97678300 H 5.34229900 -2.09356800 -2.75122900 H 3.60791300 -2.51428800 -2.64056300


23

Tbt(Dis)Ge=Te

E(RBP86) =-6005.080845au

C -2.12594600 -0.99879100 -0.09620900 C -2.82214100 0.18333200 0.24531000 C -2.07173300 1.37702800 0.28016300 C -0.68126200 1.43655600 0.02975100 C 0.01805000 0.19650600 -0.18838500 C -0.72580500 -1.02740400 -0.31416300 H -2.69097000 -1.93767000 -0.19996500 H -2.59865600 2.32113200 0.49449200 C -0.04375300 2.81251400 -0.04878200 H 1.05547600 2.69848300 -0.19650800 C -0.08830300 -2.34454400 -0.74145400 C -4.31037200 0.21685500 0.54361300 H -4.56870600 1.28447300 0.75022200 C 2.88276300 -1.12725200 1.04381800 H 2.12374400 -1.92317300 1.22939100 H 1.02246700 -2.25541200 -0.66301900 Ge 2.01068100 0.14371400 -0.22861800 Te 3.44177200 1.58367100 -1.56902900 Si 3.11293200 -0.30167500 2.78363800 Si 4.44642000 -2.01528400 0.31892400 C 4.35091800 -1.23114300 3.89111600 H 5.38501500 -1.23714300 3.49135600 H 4.37830900 -0.71746600 4.87679200 H 4.04181800 -2.28102100 4.07331400 C 3.71732600 1.48887500 2.63366000 H 3.90719200 1.90966500 3.64439700 H 4.65928100 1.55057800 2.05002200 H 2.98099700 2.14499700 2.12571800 C 1.44924300 -0.37924600 3.69618300 H 0.60315100 -0.01953000 3.07653700 H 1.22267000 -1.42336900 3.99958800 H 1.48095900 0.23399400 4.62175200 C 5.99646400 -0.92976000 0.40904300 H 6.28111600 -0.68253500 1.45263300 H 6.85319600 -1.46493700 -0.05396600 H 5.84050600 0.01918400 -0.14530200 C 4.74787200 -3.61768900 1.30423900 H 5.58526000 -4.17840800 0.83530400 H 5.01929100 -3.43358200 2.36198600 H 3.85925700 -4.28333600 1.29045200 C 4.16829400 -2.55640500 -1.48222000 H 4.05012000 -1.69084000 -2.16541100 H 5.04502600 -3.14454400 -1.82967100 H 3.27393900 -3.20751800 -1.58234500 C 0.93885300 -5.12389900 0.28668100 H 0.75045900 -5.95751300 0.99700500 H 1.06553200 -5.56515300 -0.72154500


24

H 1.90314500 -4.65592000 0.57511600 C -0.63719500 -3.33530600 2.19349300 H 0.33978500 -2.97755200 2.57834700 H -1.36791200 -2.51372300 2.33389500 H -0.95342700 -4.19152500 2.82666400 C -2.08503600 -4.79872300 -0.11199400 H -2.98920700 -4.15625400 -0.09059800 H -2.01403400 -5.24995400 -1.12354900 H -2.25609900 -5.62881500 0.60689600 C -2.12463600 -2.60966100 -3.18312700 H -2.19165800 -2.78144200 -4.27885500 H -2.73154100 -3.39167500 -2.68367400 H -2.58839500 -1.62591300 -2.96869300 C 0.41393500 -4.34280700 -3.16136800 H -0.13598700 -5.20109500 -2.72405300 H 0.34522100 -4.43482900 -4.26679600 H 1.48562500 -4.44485500 -2.89105700 C 0.64413600 -1.32658000 -3.61263800 H 0.27420100 -0.30414700 -3.39698000 H 1.72877000 -1.34444500 -3.37681400 H 0.53555300 -1.50119600 -4.70494300 C -7.14719900 0.63110700 -0.71644000 H -7.74089900 0.55871200 -1.65305100 H -7.72838300 0.13448000 0.08637400 H -7.06506700 1.70846000 -0.45882300 C -5.67022600 -2.00466000 -1.33941200 H -4.70438600 -2.53475800 -1.46924700 H -6.23513300 -2.51234000 -0.53048500 H -6.24723000 -2.13436800 -2.28013000 C -4.66658000 0.68414900 -2.50805200 H -4.66145200 1.78840300 -2.39124000 H -3.61835500 0.36215700 -2.67600900 H -5.24969800 0.44597900 -3.42299700 C -6.51703700 -0.11467200 2.75550700 H -6.68546000 0.98024500 2.67879700 H -7.29546400 -0.62167200 2.14881700 H -6.68478200 -0.40414300 3.81531000 C -3.55403400 0.08259700 3.54405300 H -2.49800300 -0.14500100 3.29033200 H -3.64771200 1.18548400 3.63597700 H -3.76743500 -0.35740000 4.54163300 C -4.63603000 -2.49693100 2.23549700 H -3.61937800 -2.85198600 1.97271500 H -4.87021800 -2.88368400 3.25064600 H -5.35317100 -2.95867300 1.52664800 C 0.51206200 5.24812500 -1.95025000 H 0.32195200 5.67021200 -2.96043800 H 0.29178100 6.04700000 -1.21167000 H 1.59299200 5.00314800 -1.88716800 C -2.39065600 4.20008900 -1.78060200 H -3.05414200 3.31264000 -1.72999700 H -2.69469300 4.90723000 -0.98465800


25

H -2.57618900 4.69381400 -2.75932400 C -0.27763100 2.52127100 -3.16738200 H 0.77290900 2.16513500 -3.20612200 H -0.94642100 1.63851300 -3.09448900 H -0.50803600 3.04182000 -4.12182200 Si -4.75222500 -0.60198500 2.23885500 Si -5.43508100 -0.15239900 -0.98653300 Si -0.49265900 -3.87678300 0.37952300 Si -0.30481900 -2.65481200 -2.65351700 Si -0.55700500 3.69502000 -1.70682200 Si -0.16027500 3.93575100 1.52639100 C -1.62911800 5.14967500 1.55199000 H -1.61812300 5.69417100 2.52106600 H -1.57414800 5.91075100 0.74639800 H -2.61106600 4.63836300 1.47257300 C 1.43391400 4.96522000 1.64243700 H 1.56667400 5.63494400 0.76899000 H 1.41241300 5.59924000 2.55473800 H 2.33345400 4.31762100 1.70467400 C -0.29976100 2.88228800 3.09737300 H -1.18158100 2.20967300 3.07191100 H 0.60029800 2.25373000 3.24634800 H -0.39858200 3.54240800 3.98571100


26

Complete citation for reference 44.

M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.

Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M.

Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L.

Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.

Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, J. E. Peralta,

F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R.

Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J.

Tomasi, M. Cossi, N. Rega, N. J. Millam, M. Klene, J. E. Knox, J. B. Cross, V.

Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J.

Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G.

Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,

O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, R. A. Gaussian 09, I.

Gaussian, Wallingford CT, 2009.


supporting information1 supporting information novel germanetellones: xyge=te (x, y=h, f, cl, br, i...

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