Experimental and Computational Studies of Nuclear Substituted 1,1

Dec 20, 2007 - Anderson, S.; Constable, E. C.; Seddon, K. R.; Turp, J. E.; Baggott, J. E.; ..... Radicals in Organic Chemistry; John Wiley & Sons: New...
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Experimental and Computational Studies of Nuclear Substituted 1,1’-Dimethyl-2,2’Bipyridinium Tetrafluoroborates Dong Zhang,2 João P. Telo,1 Chen Liao,2 Sean E. Hightower,2 Edward L. Clennan*2 Department of Chemistry University of Wyoming Laramie, WY 82071 USA Instituto Superior Técnico Química Orgânica Av. Rovisco Pais 1049-001 Lisboa, Portugal SUPPORTING INFORMATION S2 Table S1. S3 Table S2. S4 Table S3. S5 Table S4. S6 Table S5. S7 Table S6. S8 Table S7. S9. Table S8. S10. Table S9. S11. Table S10. S12. Table S11. S13. Table S12. S14. Table S12 S15. Table S13. S16. S17. S18.

1 2

Bipyridinium Dication Energy and Structural Data as a Function of Basis Set and Theory. 2,2’-Bipyridinium-Radical Cation, and Neutral Redox Partners B3LYP631G(d). 1,1’-Dimethyl-2,2’-bipyridinium Dication, Radical Cation, and Neutral B3LYP/6-31G(d) Structural and Energy Data. 1,1’-Dimethyl-4,4’-dichloro-2,2’-bipyridinium Dication, Radical Cation, and Neutral B3LYP/6-31G(d) Structural and Energy Data. 1,1’-Dimethyl-4,4’-dicarbomethoxy-2,2’-bipyridinium Dication B3LYP/631G(d) Structural and Energy Data. 1,1’-Dimethyl-4,4’-dicarbomethoxy-2,2’-bipyridinium Radical Cation B3LYP/6-31G(d) Structural and Energy Data. Direduced 1,1’-Dimethyl-(ii)-4,4’-dicarbomethoxy-2,2’-bipyridinium B3LYP/6-31G(d) Structural and Energy Data. 1,1’-Dimethyl-4,4’-dimethylamino-2,2’-bipyridinium Dication and Radical Cations B3LYP/6-31G(d) Structural and Energetic Data. Direduced 1,1’-Dimethyl-4,4’-dimethylamino-2,2’-bipyridinium B3LYP/631G(d) Energy and Structural Data. 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium Dication B3LYP/6-31G(d) Energy and Structural Data. 1,1’-Dimthyl-4,4’-dimethoxy-2,2’-bipyridinium Radical Cations B3LYP/631G(d) Energy and Structural Data. Direduced 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium B3LYP.6-31G(d) Energy and Structural Data. (continued). Direduced 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium B3LYP.6-31G(d) Energy and Structural Data. Direduced 1,1’-Dimethyl-4-(i)-carbomethoxy-4’-(o)-methoxy-2,2’bipyridinium B3LYP/6-31G(d) Structural and Energetic Data. Hammett Plot for Reduction of Substituted 1,1’-Dimethyl-2,2’-bipyridinium Dications. Experimental (red) and computer fit (blue) dynamic proton NMR spectra of two N-methyl groups in 32+. UV-Vis Spectrum of 1,1’-dimethyl-4,4’-bismethoxy-2,2’-bipyridinium radical cation in CH3CN

Instituto Superior Técnico University of Wyoming

Table S1. Bipyridinium Dication Energy and Structural Data as a Function of Basis Set and Theory 4

6

Erel(kcal/mol) dC2-C2’ dN1-C2 dC3-H dN1-H >N1C2C2’N2 >C2C2’C3 >N1C6C5 >C2C3H >C2N1H >C2’C2N1 >HN1C2C2’

acc 0 1.484 1.366 1.085 1.019 136.19 124.09 119.68 120.09 118.84 117.80 4.19

N

1' 6'

N

2

5

aca,b 0 1.516 1.373 1.084 1.034 138.1 123.3 119.8 120.6 119.9 117.1

H

3

5'

2'

1H

3'

4'

acd

ace,f

1.478 1.363 1.087 1.025 127.35 124.11 119.11 119.72 118.66 117.66 3.78

1.479 1.363 1.083 1.020 124.99 123.89 119.23 119.57 118.78 117.78 3.82

sca,g 2.10 1.518 1.375 1.085 1.033 54.2 121.8 119.8 120.1 122.1 118.5

scb 1.78 1.489 1.368 1.085 1.019 59.45 122.71 119.66 119.61 119.26 119.05 3.62/3.61

a. STO-3G with partial geometry optimization-Hofmann, H.-J.; Cimiraglia, R.; Tomasi, J. J. Mol. Struc. (Theochem) 139, 213-219(1986). b. ac-anticlinal; torsion angle about C2-C2’ between +90o and +1500 or between -150o and -90o. c. B3LYP/6-31G(d). d. MP2/6-31G(d). e. MP2/6-31+G(d,p). f. geometry optimization only. g. sc-synclinal;; torsion angle about C2-C2’ between +30o and +900 or between -90o and -30o.

S2

Table S2. 2,2’-Bipyridinium Radical Cation, and Neutral Redox Partners B3LYP/6-31G(d) Structural and Energy Data. 4

3

H 1' N

2 2'

5 6

N 1H

4

6' 5'

3'

4'

3

3'

4'

4

2

5

5' 6

N

2' N 1'

1H H

6'

Z

E (hartrees) Erel (kcal/mol) Symmetrye Dipole Moment >N1C2C2’N1’ dC2C2’ dHN1 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N >HN1C2C2’

Radical Cation apa -496.34585864 0 C2 17.9339 165.57 1.423 1.011 1.421 1.375 1.422 1.367 1.365 5.96/5.95

Radical Cation spb -496.34382338 1.28 C2 16.0741 16.75 1.425 1.013 1.417 1.376 1.424 1.364 1.373 17.50/17.46

3

H 1' N 2

N

2'

5 6

3'

1H

6' 5' 4'

E

Z-Neutral -496.52171753 0 C2 1.7262 2.83 1.377 1.017 1.440 1.359 1.450 1.351 1.390 36.09/35.95

E-Neutral -496.51714084 2.87 Ci 0.0033 179.99 1.373 1.008 1.450 1.358 1.448 1.356 1.373 25.14/25.25

a. ap-antiperiplanar; torsion angle about C2-C2’ between -150o and +150o. b. sp-synperiplanar; torsion angle about C2-C2’ between -30o and +30o.

S3

Table S3. 1,1’-Dimethyl-2,2’-bipyridinium Dication, Radical Cation, and Neutral B3LYP/6-31G(d) Structural and Energy Data 4

1'

3 2 2'

5 6

N 1

Dication E (hartrees) Erel (kcal/mol) Symmetrye Dipole Moment >N1C2C2’N1’ dC2C2’ dCH3N1 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N >CH3N1C2C2’

-574.63265213 C2 32.3932 98.48 1.501 1.491 1.388 1.401 1.392 1.388 1.355 1.83/1.86

N 3'

4

6' 5' 4'

Radical Cation aca -574.95748666 0 C2 16.56 140.82 1.445 1.473 1.414 1.377 1.418 1.366 1.374 17.24/17.00

1'

3 2 2'

5 6

N 1

N 3'

4

6' 5' 4'

Radical Cation scb -574.95500476 1.56 C1 16.4926 44.43 1.446 1.474/1.476 1.410/1.412 1.379 1.417/1.420 1.367/1.366 1.376/1.377 20.85/28.37

1'

3

N

2

5 6

N 1

2' 3'

6' 5' 4'

Z-Anti-Neutralc

E-Anti-Neutralc

E-(pp)-Neutrald

-575.12855563 0 C2 1.7006 17.25 1.392 1.464 1.447 1.358 1.444 1.351 1.391 46.34/46.41

-575.12339951 3.24 Ci 0.004 179.99 1.375 1.471 1.451 1.358 1.446 1.354 1.392 64.12/64.23

-575.12435836 2.63 C1 2.0618 158.72 1.392 1.467/1.454f 1.466/1.446f 1.361/1.359f 1.447/1.438f 1.350/1.355f 1.399/1.381f 66.92/16.63

a. ac-anticlinal; torsion angle about C2-C2’ between +90o and +1500 or between -150o and -90o. b. sc-synclinal; torsion angle about C2-C2’ between 30o and 90o or -30o and -90o. c. syn and anti refer to the placement of the N1 and N1’ methyl groups relative to the plane defined by the C2-C2’ double bond and the four attached atoms. d. push-pull conformation; see text. e. approximate point group symmetry. f. N-methyl group most closely eclipsed with C2C2’ bond or ring bond in ring with N-methyl group most closely eclipsed with C2C2’ bond.

S4

Table S4. 1,1’-Dimethyl-4,4’-dichloro-2,2’-bipyridinium Dication, Radical Cation, and Neutral B3LYP/6-31G(d) Structural and Energy Data Cl

1'

3

4 5

2 2' 6

N 1

N 3'

Cl 6' 5' 4'

Cl

4 5

1'

3 2 2'

6

N 1

N

Cl 6' 5'

3'

4'

Cl

4 5

1'

3 2 2'

6

N

N 3'

1

6' 5' 4'

Cl

E

4 5

3

3' 2 2'

6

N

N

1

1'

Cl 4' 5' 6'

Z c

E-Anti-Neutral

E-(pp)-Neutrald

Radical Cation scb -1494.13514990 1.63 C1 5.6007

Z-Anti-Neutral

C1 5.7298

Radical Cation aca -1494.13774005 0 C2 3.5124

-1494.32201828 0 C2 5.0498

-1494.31780767 2.64 Ci 0.0047

-1494.31862449 2.13 C1 3.0231

97.06 1.502 1.703 1.490 1.373 1.383 1.410 1.400 1.382 1.358 1.20

141.35 1.445 1.730 1.474 1.402 1.413 1.378 1.420 1.364 1.373 17.23

45.18 1.447 1.728 1.475/1.477 1.401/1.400 1.409/1.408 1.381 1.422/1.421 1.364/1.365 1.376/1.375 22.61/27.72

15.87 1.390 1.758 1.466 1.436 1.448 1.355 1.442 1.352 1.387 47.35/47.40

179.99 1.374 1.759 1.473 1.440 1.451 1.354 1.444 1.355 1.387 63.59/63.72

159.77 1.391 1.757/1.761 1.456/1.469 1.428/1.451 1.446/1.447 1.356/1.357 1.436/1.444 1.355/1.350 1.377/1.394 14.94/67.12

Dication E (hartrees) Erel (kcal/mol) Symmetrye Dipole Moment >N1C2C2’N1’ dC2C2’ dC4Cl dCH3N1 dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N >CH3N1C2C2’

Cl

-1493.80954021

a. ac-anticlinal; torsion angle about C2-C2’ between +90o and +1500 or between -150o and -90o b. sc-synclinal; torsion angle about C2-C2’ between 30o and 90o or -30o and -90o. c. Anti-refers to placement of N-Methyl groups relative to approximate plane defined by NC2C2’N dihederal angle. d. push-pull conformation; see text. e. Approximate higher order point group. S5

Table S5. 1,1’-Dimethyl-4,4’-dicarbomethoxy-2,2’-bipyridinium Dication B3LYP/631G(d) Structural and Energy Data. OCH3 O

3

4 5

2 2' 6

N 1

O

O 1'

N

H3CO

6'

5' 4'

3'

O

3

4 5

2 2' 6

N

Energy a.u. Erel(kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4(C=O) dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dN-CH3 >CH3NC2C2’ >C3C2C2’C3’ >CH3NC2 >O=CC4C3 >CH3OC(O)C4 >CH3OC=O

6'

N

5' 4'

3'

1

o-o H3CO

H3CO

1'

i-i

o-oa -1030.38633158 3.02 C2 6.6111Debye 99.37 1.500 1.516 1.372 1.388 1.403 1.394 1.385 1.356 1.490 1.96 91.85 121.15 179.55 179.64 0.38

O

OCH3

i-i -1030.39115018 0 C2 7.5256 109.77 1.499 1.517 1.374 1.385 1.402 1.394 1.388 1.355 1.491 3.91 100.50 121.48 2.48 179.82 0.31

1'

3

4 5

2 2' 6

N 1

N

6'

3'

5' 4'

O

i-o H3CO

i-o -1030.38863601 1.58 C1 7.7829Debye 103.74 1.500 1.517b/1.516c 1.374b/1.372c 1.384b/1.388c 1.402b/1.403c 1.394b/1.394c 1.388b/1.385c 1.355b/1.356c 1.490b/1.490c 2.84b/2.69c 95.45 121.19b/121.32c 1.83b/179.69c 179.93b/179.42c 0.20b/0.57c

a. o-carbonyl group facing out away from the adjacent pyridinium ring; i- carbonyl group facing in towards the adjacent pyridinium ring. b. in. c. out

S6

Table S6. 1,1’-Dimethyl-4,4’-dicarbomethoxy-2,2’-bipyridinium Radical Cation B3LYP/3-21G(d) Structural and Energy Data. OCH3 O 4 5

N

2 6

N

6' 5' 4'

2'

1

H2CO

3'

O

o-o H3CO

Energy a.u. Erel(kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4(C=O) dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dN-CH3 >CH3NC2C2’ >C3C2C2’C3’ >CH3NC2 >O=CC4C3 >CH3OC(O)C4 dCH3OC=O

O

O 1'

3

(o-o)aca -1030.71320090 2.01 C2 3.6703 138.29 1.454 1.494 1.396 1.405 1.385 1.420 1.364 1.377 1.473 15.78/15.75 125.41 122.45/122.44 178.26/178.25 179.70/179.71 0.62

(i-i)ac -1030.71640238 0 C2 3.9664 140.22 1.453 1.494 1.398 1.402 1.384 1.420 1.366 1.375 1.474 15.68 127.28 122.58 2.35/2.33 179.83/179.82 0.16

4 5

N

6'

N

2 6

H3CO

1'

3

5' 2'

4'

3'

1

i-i

O

N

2 6

OCH3

(i-o)ac -1030.71475337 1.03 C1 5.3377 139.35 1.453 1.494c/1.494d 1.398c/1.395d 1.402c/1.406d 1.385c/1.385d 1.420c/1.419d 1.365c/1.364d 1.376c/1.376d 1.473c/1.475d 16.49c/15.24d 126.38 122.46c/122.58d 2.44/178.29d 179.68c/179.69d 0.032c/0.65d

1'

3

4 5

N 1

6' 5'

2' 3'

4'

O

i-o H3CO

(o-o)scb -1030.71046449 3.73 C1 3.2481 47.52 1.455 1.495/1.493 1.396/1.397 1.402/1.403 1.387/1.387 1.419/1.421 1.365/1.364 1.377/1.379 1.474/1.476 19.15/26.72 50.22 120.25/120.91 178.66/178.04 179.86/179.88 0.051/0.092

(i-i)sc -1030.71194609 2.80 C1 6.1211 47.54 1.455 1.496/1.494 1.397/1.398 1.399/1.400 1.387 1.419/1.421 1.367/1.366 1.376/1.378 1.474/1.475 19.44/26.63 49.80 120.17/120.77 0.087/0.456 179.59/179.64 0.204/0.200

(i-o)sc -1030.71141820 3.13 C1 5.1148 47.27 1.455 1.493c/1.496d 1.398c/1.395d 1.400c/1.402d 1.387c/1.387d 1.422c/1.418d 1.365c/1.366d 1.378c/1.376d 1.475c/1.474d 27.18c/19.06d 49.71 120.86c/120.22d 1.33/178.60 179.74c/179.53d 0.054c/0.23d

a. ac-anticlinal; torsion angle about C2-C2’ between +90o and +1500 or between -150o and -90o b. sc-synclinal; torsion angle about C2-C2’ between 30o and 900 or -300 and -900. c. in. d. out.

S7

Table S7. Direduced 1, 1’-Dimethyl-(ii)-4,4’-dicarbomethoxy-2,2’-bipyridinium B3LYP/6-31G(d) Structural and Energetic Dataa O H3CO

O 1'

3

4 5

N

2 6

N 1

5'

2' 3'

E(i-i)Anti O

Energy a.u.b Erel(kcal/mol) Symmetrya Dipole Moment >N1C2C2’N1’ dC2C2’ dC4(C=O) dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dN-CH3 >CH3NC2C2’ >C3C2C2’C3’ >CH3NC2 >O=CC4C3 >CH3OC(O)C4 >CH3OC=O

H3CO

6' 4'

4 5

OCH3

N

2 6

O

O 1'

3

N 1

H3CO

6' 5'

2' 3'

E(i-i)pp O

4 5

4'

N 1

H3CO

6'

N

2 6

OCH3

1'

3

5'

2'

4'

3'

E(i-i)Syn O

4 5

3'

N 1

2'

OCH3 4' 5'

2 6

OCH3

O 3

N

1' 6'

Z(i-i)Anti

E(i-i)Anti -1030.88897471 5.65 Ci 0.0018

E(i-i)pp -1030.89507870 1.82 C1 2.8616

E(i-i)Syn -1030.89545345 1.59 C2 2.2912

Z(i-i)Anti -1030.89798549 0 C2 5.6264

180.00 1.390 1.481 1.434 1.433 1.368 1.449 1.352 1.393 1.474 62.49/62.46 180.00 119.69(8) 0.80 179.57(6) 0.00(1)

153.71 1.414 1.479/1.470 1.418/1.437 1.422/1.416 1.373/1.377 1.441/1.450 1.354/1.349 1.384/1.400 1.456/1.468 12.91/59.81 144.18 121.70/118.44 2.10/3.68 179.73/179.88 0.27/0.25

151.20 1.414 1.473 1.426 1.417 1.376 1.446 1.352 1.388 1.458 28.84/28.66 140.73 121.66 2.91 179.72 0.14/0.13

25.01 1.415 1.475 1.424 1.420 1.373 1.447 1.350 1.395 1.463 40.78/40.99 31.54 117.82/117.80 1.52/1.28 179.99/179.74 0.055/0.102

a. i-i (in-in) both carbonyl oxygens are pointing in towards the appended heterocyclic ring. b. energy in Hartrees. c. approximate higher-order point groups.

S8

Table S8. 1,1’-Dimethyl-4,4’-dimethylamino-2,2’-bipyridinium Dication and Radical Cations B3LYP/6-31G(d) Structural and Energetic Data. N

2 2' 6

E (hartrees) Erel (kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4N dCH3N1 dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N Amino angle 1e Amino angle 2e Amino angle 3e Sum Amino angles >CH3NC4C3 dNCH3 >CH3N1C2C2’

1'

3

4 5

N 1

N 3'

N 6'

4 5

5' 4'

Dication -842.65330313 C2 2.8778 86.63o 1.501Å 1.337Å 1.480Å 1.377Å/1.376Å 1.372Å/1.373Å 1.437Å 1.429Å/1.430Å 1.366Å 1.366Å/1.367Å 120.31 118.80 120.89 360 179.72/2.46o 1.475/1.472Å 1.70/3.22o

2 2' 6

N

1'

3

N 1

N 3'

Radical Cation aca -842.91996581 0 C2 1.6187 142.20 1.441 1.363 1.468 1.409 1.412 1.400 1.441 1.359 1.370/1.369 119.85 119.28 120.68 359.81 173.48/1.55 1.462c/1.458d 19.63/20.37

6' 5' 4'

N

Radical Cation scb -842.91956283 0.25 C2 1.3640 40.85 1.441 1.362 1.472 1.409 1.409 1.402 1.443 1.357 1.374 119.81 119.38 120.74 359.93 174.84/2.38 1.462c/1.458d 29.57/28.44

a. ac-anticlinal; torsion angle about C2-C2’ between +90o and +1500 or between -150o and -90o b. sc-synclinal; torsion angle about C2-C2’ between 30o and 900 or -30o and -900. c. N-methyl anti to C3-C4 bond. d. N-methyl syn to C3-C4 bond. e. angles about around dimethylamino group; amino (e.g. angle 1 >C4NCH3). These will equal 360o for a perfectly planar dimethylamino group.

S9

Table S9. Direduced 1,1’-Dimethyl-4,4’-dimethylamino-2,2’-bipyridinium B3LYP/6-31G(d) Energy and Structural Data N 4 5

1'

3 2 2'

6

N 1

N 3'

6' 5' 4'

N 4 5

N

E-Anti

E (hartrees) Erel (kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ C4N dCH3N1 dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N Amino angle 1d Amino angle 2d Amino angle 3d Sum Amino angles >CH3NC4C3

E-Antia -843.05789854 2.93 Ci 0.0005 180.00 1.375 1.410 1.471 1.443 1.451 1.368 1.461 1.350 1.388 117.22 112.36 116.80 346.38 133.65b/3.99c

dNCH3 >CH3N1C2C2’

1.460b/1.451c 66.03

1'

3 2 2'

6

N 1

N 3'

N 6' 5' 4'

4 5

2 2' 6

N

1'

3

N 1

E-Syn

N 3'

E-pp

E-Syn -843.05724394 3.34 C1 0.8679 160.82 1.382 1.410/1.408 1.466/1.468 1.446/1.444 1.448/1.446 1.369 1.458/1.457 1.349 1.389/1.387 116.65 112.33 117.11 346.09 132.16b/5.10c 131.62b/7.02c 1.466/1.468 52.78/55.55

6' 5' 4'

N

N 4 5

3

3' 2 2'

6

N

N

1

1'

N 4' 5' 6'

Z-Anti

E-pp -843.05514914 4.65 C1 2.4910 161.30 1.393 1.441e/1.403f 1.465e/1.455f 1.455e/1.425f 1.446e/1.446f 1.361e/1.371f 1.457e/1.448f 1.349e/1.353f 1.400e/1.375f 113.20e/118.15f 111.71e/112.77f 113.28e/117.48f 338.19e/348.40 119.88e/111.63f 135.29b,e/5.36c,e 1.465e/1.455f 69.06e/14.12f

Z-Anti -843.06256050 0 C1 0.9244 8.58 1.384 1.411/1.412 1.465/1.466 1.441/1.439 1.455/1.454 1.366 1.457/1.458 1.349 1.387/1.385 117.16 112.35 116.98 346.49 130.92b/6.17c 130.17b/7.62c 1.460b/1.451c 53.67/51.64

a. syn and anti refer to the placement of the N1 and N1’ methyl groups relative to the plane defined by the C2-C2’ double bond and the four attached atoms. b. Nmethyl anti to C4-C3 bond. c. N-methyl syn to C4-C3 bond. d. angles about around dimethylamino group; amino (e.g. angle 1 >C4NCH3). These will equal 360o for a perfectly planar dimethylamino group. e. on/in ring with N1-methyl deviating most from approximate plane defined by N1C2C2,N1. f. on/in ring with N1methyl deviating the least from approximate plane defined by N1C2C2,N1.

S10

Table S10. 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium Dication B3LYP/631G(d) Energy and Structural Data. O 4 5

1'

3 2 2'

6

N

N 3'

1

O 6' 5' 4'

O

4 5

2 2' 6

N

N

O 6' 5'

3'

1

o-o

E (hartrees) Erel(kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4O dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dCH3O >CH3OC4 >CH3OC4C3 dNCH3 >CH3N1C2C2’

1'

3

4'

O

4 5

2 2' 6

i-i

o-oa -803.72128420 0 C2 2.9837 93.44 1.501 1.309 1.379 1.373 1.422 1.411 1.377 1.359 1.456 121.08 179.43 1.485 0.03

1'

3

N

N 3'

1

6' 5' 4'

O

i-o

i-i -803.71475950 4.09 C2 1.598 91.09 1.503 1.310 1.370 1.381 1.420 1.413 1.370 1.366 1.451 121.89 0.33 1.486 0.76

i-o -803.71807718 2.01 C1 3.169 90.36 1.502 1.310b/1.309c 1.370b/1.379c 1.381b/1.373c 1.420b/1.423c 1.413b/1.411c 1.370b/1.377c 1.366b/1.359c 1.451b/1.456c 121.83b/121.13c 0.80b/179.75c 1.486b/1.485c 1.17b/0.39c

a. o-methyl on methoxy group facing out away from the adjacent pyridinium ring; i- methyl on methoxy group facing in towards the adjacent pyridinium ring. b. on/in ring with in-methoxy group. c. on/in ring with out-methoxy group.

S11

Table S11. 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium Radical Cations B3LYP/6-31G(d) Energy and Structural Data. O 4

1' 6'

3 2 2'

5

N

6 1

N 3'

5' 4'

O

i-i

E (hartrees) Erel(kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4O dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dCH3O >CH3OC4C3 dNCH3 >CH3N1C2C2’

(o-o)aca -804.01267699 0.77 C1 1.526 143.20 1.440 1.341 1.410 1.411 1.386 1.428 1.364 1.368 1.434 176.53 1.472 18.04

(i-i)ac -804.01389778 0 C2 1.287 142.25 1.441 1.339 1.403 1.419 1.384 1.429 1.359 1.374 1.431 1.96/1.99 1.472 19.12/19.07

(i-o)ac -804.01324591 0.41 C1 2.688 142.42 1.440 1.339c/1.341d 1.403c/1.410d 1.419c/1.410d 1.384c/1.386d 1.428c/1.428d 1.359c/1.364d 1.373c/1.368d 1.430c/1.434d 1.91c/176.73d 1.472c/1.471d 17.60c/19.45d

(o-o)scb -804.01040858 2.19 C2 3.454 42.50 1.443 1.340 1.409 1.406 1.388 1.429 1.363 1.373 1.434 177.90 1.474 27.51/27.49

(i-i)sc -804.01269983 0.75 C2 1.256 42.32 1.442 1.338 1.403 1.415 1.386 1.430 1.358 1.377 1.432 2.64 1.475 27.31/27.36

(i-o)sc -804.01181291 1.31 C1 3.161 42.17 1.442 1.338c/1.340d 1.403c/1.409d 1.415c/1.406d 1.386c/1.388d 1.430c/1.429d 1.358c/1.364d 1.378c/1.372d 1.432c/1.434d 3.07c/177.46d 1.475c/1.474d 28.41c/26.59d

a. ac-anticlinal; torsion angle about C2-C2’ between +90o and +1500 or between -150o and -90o b. sc-synclinal; torsion angle about C2-C2’ between 30o and 90o or -30o and -90o. c. in/on ring with in-methoxy group. d. in/on ring with out-methoxy group.

S12

Table S12. Direduced 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium B3LYP/6-31G(d) Energy and Structural Data O 4

3'

3 2 2'

5 6

N

O

O

N

1

E(hartrees) Erel(kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4O dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dCH3O >CH3OC4C3 dNCH3 >CH3N1C2C2’

O

O

N N

1' 6'

N

N

N

O

Z-(o-o) c

O

4' 5'

E-(o-o)anti

Z-(i-o)

E(o-o)syna -.16056042 9.49 C2 0.883

E(o-o)antib -.16329033 7.78 Ci 0.003

E(i-i)syn -.17006881 3.52 C2 1.468

E(i-i)anti -.17248924 2.00 Ci 0

E(i-o)syn -.16522803 6.56 C1 2.581

159.74 1.381 1.372 1.448 1.445 1.362 1.448 1.354 1.383 1.416 177.31 1.466 51.49/51.56

180.00 1.373 1.371 1.445 1.451 1.361 1.451 1.356 1.382 1.418 170.24 1.470 63.05/62.98

161.53 1.378 1.365 1.446 1.452 1.362 1.448 1.349 1.389 1.417 0.88 1.468 55.22/55.24

180.00 1.372 1.365 1.443 1.446 1.361 1.450 1.351 1.389 1.417 1.09 1.470 65.70/65.69

161.10 1.379 1.365d/1.372e 1.445d/1.450e 1.452d/1.445e 1.362d/1.362e 1.447d/1.449e 1.350d/1.353e 1.387d/1.385e 1.416d/1.416e 0.97d/178.10e 1.468d/1.467e 53.35d/54.78e

E(i-o)anti -.16779896 4.95 C1 2.356

N O E-(i-i)syn

Z(o-o) -.16614321 5.98 C2 2.912

179.86 10.37 1.372 1.383 d e 1.365 /1.371 1.373 1.442d/1.446e 1.443 1.456d/1.451e 1.450 1.361d/1.360e 1.359 d e 1.449 /1.451 1.449 1.352d/1.355e 1.353 1.386d/1.384e 1.384 d e 1.417 /1.418 1.416 1.12d/170.38e 172.02/171.41 1.471d/1.470e 1.466 63.37d/65.34e 51.34/51.33

Z(i-i) -.17568029 0.00c C2 0.174

Z(i-o) -.17113696 2.85 C1 2.478

7.54 1.380 1.366 1.440 1.458 1.360 1.448 1.350 1.386 1.416 1.68/1.69 1.466 53.25

9.07 1.381 1.366d/1.372e 1.441d/1.442e 1.457d/1.452e 1.359d/1.359e 1.448d/1.449e 1.349d/1.354e 1.388d/1.382e 1.417d/1.417e 1.44d/171.78e 1.466d/1.466e 53.16d/51.27e

a. N-methyl groups on same face of plane roughly defined by N1C2C2’N1’. b. N-methyl groups on opposite face of plane roughly defined by N1C2C2’N1’. c. Energy 804.xxxxxxx a.u. d. in/on ring with in-methoxy group. e. in/on ring with out-methoxy group

S13

Table S12 (Continued). Direduced 1,1’-Dimethyl-4,4’-dimethoxy-2,2’-bipyridinium B3LYP/6-31G(d) Energy and Structural Data O 4

3'

3 2 2'

5 6

N

O

1' 6'

Z-(o-o)

E (hartrees) Erel(kcal/mol) Symmetry Dipole Moment >N1C2C2’N1’ dC2C2’ dC4O dNCH3 dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dCH3O >CH3OC4C3 >CH3N1C2C2’ >CH3N1C2

O

O

E(o-o)-(pp)a -804.16270599 8.14 C1 1.9284 162.70 1.387 1.378e/1.369f 1.465e/1.455f 1.456e/1.435f 1.452e/1.447f 1.361e/1.362f 1.450e/1.442f 1.352e/1.357f 1.389e/1.372f 1.415e/1.417f 168.26e/176.00f 67.96e/15.4f 117.43e/121.14f

O

N

4' 5'

N

1

O

N

N

N

N

O E-(o-o)anti

Z-(i-o)

E(i-i)-(pp) -804.17141066 2.68 C1 1.8343 161.98 1.384 1.371e/1.364f 1.467e/1.455f 1.454e/1.432f 1.458e/1.453f 1.361e/1.362f 1.450e/1.441f 1.348e/1.352f 1.394e/1.378f 1.414e/1.418f 1.90e/1.37f 68.06e/20.99f 116.90e/121.12f

E(i-o)b-(pp) -804.16657472 5.71 C1 3.8495 161.79 1.385 1.371c/1.370d 1.466c/1.455d 1.453c/1.437d 1.458c/1.447d 1.361c/1.362d 1.449c/1.443d 1.348c/1.356d 1.391c/1.374d 1.413c/1.417d 2.00c/176.11d 66.73c/20.70d 117.24c/121.07d

N O E-(i-i)syn

E(o-i)-(pp)g -804.16737584 5.21 C1 1.3776 162.72 1.386 1.378d/1.363c 1.466d/1.455c 1.457d/1.430c 1.452d/1.453c 1.361d/1.362c 1.450d/1.440c 1.352d/1.353c 1.391d/1.377c 1.415d/1.418c 167.80d/1.34c 69.22d/16.06c 117.07d/121.20c

a. pp-push pull conformation. b. i-methoxy is on ring with the N-methyl group that deviates the most from the approximate plane defined by N1C2C2’N1’ atoms. c. in/on ring bearing in-methoxy. d. in/on ring bearing out-methoxy. e. on/in ring with N-methyl that deviates the most from the approximate plane defined by N1C2C2’N1’ atoms. f. on/in ring with N-methyl that deviates the least from the approximate plane defined by N1C2C2’N1’ atoms. g. o-methoxy is on ring with the N-methyl group that deviates the most from the approximate plane defined by N1C2C2’N1’ atoms.

S14

Table S13. Direduced 1, 1’-Dimethyl-4-(i)-carbomethoxy-4’-(o)-methoxy-2,2’-bipyridinium B3LYP/6-31G(d) Structural and Energetic Dataa O H3CO

3

4 5

4' 5'

2 6

N 1

2'

N

1' 6'

Z(i-o)Anti

Energy a.u.b Erel(kcal/mol) Symmetryc Dipole Moment >N1C2C2’N1’ dC2C2’ dC4(C=O) dC4’O

dN-C2 dC2-C3 dC3-C4 dC4-C5 dC5-C6 dC6-N dN-CH3 dCH3O

>CH3NC2C2’ >C3C2C2’C3’ >CH3NC2 >CH3OC4C3

>O=CC4C3 >CH3OC(O)C4 >CH3OC=O

O

O

3'

E(i-o)-ppa -917.53460620 0.29 C1 6.12924 157.96o 1.408Å 1.464Å 1.361Å 1.450Åd/1.420Åe 1.418Åd/1.433Åe 1.376Åd/1.369Åe 1.456Åd/1.435Åe 1.345Åd/1.360Åe 1.412Åd/1.370Åe 1.467Åd/1.461Åe 1.421Å 68.68od/11.11oe 150.06o 115.61od/121.78oe 177.15o 3.90o 179.69o 0.26o

3'

4' 5' 6'

1

N

2'

N 1'

6 5

2 3

E(i-o)pp O

4

OCH3

Z(i-o)-ppa -917.53506312 0 C1 6.4227 22.69o 1.408Å 1.466Å 1.363Å 1.443Åd/1.423Åe 1.419Åd/1.434Åe 1.374Åd/1.368Åe 1.456Åd/1.439Åe 1.345Åd/1.357Åe 1.411Åd/1.374Åe 1.467Åd/1.466Åe 1.420Å 56.20od/31.86oe 26.60o 115.42od/119.35oe 179.04o 2.54o 180.0o 0.11o

a. i-o (in-out) carbonyl oxygen pointing in towards the appended heterocyclic ring and the methoxy methyl pointing out away from the appended heterocyclic ring. b. energy in Hartrees. c. approximate higher-order point groups. d. in or on carbomethoxy substituted ring. e. in or on methoxy substituted ring. S15

Hammett Plot For Reduction of Substituted 1,1'-Dimethyl-2,2'bipyridinium Dications 0

-0.2

6

y = 0.9796x - 0.7508 R2 = 0.9845 -0.4

-0.6

4 2

-0.8

5 -1

-1.2

3 -1.4

-1.6 -0.8

-0.6

-0.4

-0.2

0

Hammett Sigma Value (σp)

S16

0.2

0.4

0.6

Experimental (red) and computer fit (blue) dynamic proton NMR spectra of two N-methyl groups in 32+.

S17

1.8 1.6

UV-Vis Spectrum of 1,1'-dimethyl-4,4'-bismethoxy-2,2'-bipyridinium radical cation in CH3CN 249 nm (ε=20180 Lmole-1cm-1)

1.4 1.2 1 H3CO

0.8

N

0.6 N

0.4

328 nm (ε=4745 Lmole-1cm-1)

0.2 0 200

OCH3

554 nm (ε=1220 Lmole-1cm-1)

400

600

800 Wavelength (nm)

S18

1000

1200

1400