Eur. J. Org. Chem. 2008 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008 · ISSN 1434–193X

SUPPORTING INFORMATION

Title: New Push-Pull Chromophores Featuring TCAQ (11,11,12,12-Tetracyano-9,10-anthraquinodimethane) and Other Dicyanovinyl Acceptors Author(s): Filip Bureš, W. Bernd Schweizer, Corinne Boudon, Jean-Paul Gisselbrecht, Maurice Gross, François Diederich* Ref. No.: O200700970

Experimental procedures and spectral characterization:

2-(9,10-Dioxo-9,10-dihydroanthracen-2-yl)-1,1,3,3-

tetramethylguanidine (16). To a solution of tetramethylurea

(1.07 mL, 8.96 mmol) in benzene (30 mL), phosphoryl

trichloride (0.84 mL, 8.96 mmol) was added dropwise and the

mixture stirred for 12 h at 20 °C. 2-Aminoanthracene-9,10-

dione (2.0 g, 8.96 mmol) in benzene (30 mL) was added and the

mixture heated to reflux for 6 h. After cooling to 20 °C, the

upper benzene layer was discarded and the bottom oily layer

poured on water (300 mL), neutralized with NaOH, extracted

with EtOAc (3 × 100 mL), dried (MgSO4) and concentrated in

vacuo to afford a crude solid. This solid was extracted again

with Et2O (2 × 100 mL), and evaporation of the combined organic

layers furnished 1.5 g (52%) of 16 as an orange solid. M.p.

147–148 °C; 1H NMR (300 MHz, CDCl3, 25 °C): δ = 2.75 (s, 12H,

NCH3), 7.02 (dd, 3JH,H = 9.0 Hz, 4JH,H = 3.0 Hz, 1H, AQ), 7.36

(d, 4JH,H = 3.0 Hz, 1H, AQ); 7.64–7.74 (m, 2H, AQ), 8.12 (d,

3JH,H = 9.0 Hz, 1H, AQ), 8.17–8.26 (m, 2H, AQ) ppm; 13C NMR (75

MHz, CDCl3, 25 °C): δ = 39.74, 118.04, 125.18, 126.69, 126.81,

126.84, 129.00, 133.05, 133.63, 133.72, 134.10, 134.61,

158.56, 161.46, 181.98, 184.19 ppm; IR (neat): ν = 2861, 1666,

1645, 1587, 1509, 1460, 1403, 1386, 1352, 1323, 1278, 1139,

1097, 1018, 900, 848, 803, 771, 727, 714, 671, 617 cm-1;

UV/Vis (CH2Cl2): λmax (ε) = 447 (6500), 309 (sh, 24300), 246 nm

(27400 mol-1dm3cm-1); HR-FT-MALDI-MS (DCTB) m/z: calcd for

C19H20N3O2+: 322.1550; found 322.1549 (MH+).

2',2'-(9,10-Dioxo-9,10-dihydroanthracene-2,6-diyl)bis(1,1,3,3-

tetramethylguanidine) (17). The title compound was

synthesized from tetramethylurea (0.5 mL; 4.2 mmol),

phosphoryl trichloride (0.4 mL, 4.2 mmol), and 2,6-

diaminoanthracene-9,10-dione (500 mg, 2.1 mmol) in a similar

manner to 16. The red precipitate formed after neutralization

was filtered, washed with water, air-dried, and extracted with

CHCl3 (3 × 100 mL). Evaporation of the combined organic layers

furnished 210 mg (23%) of 17 as an orange solid. M.p. 223–224

°C [lit.[1] m.p. 227 °C]; 1H NMR (300 MHz, CDCl3, 25 °C): δ =

2.78 (s, 24H, NCH3), 7.02 (dd, 3JH,H = 9.0 Hz, 4JH,H = 3.0 Hz,

2H, AQ), 7.36 (d, 4JH,H = 3.0 Hz, 2H, AQ), 8.11 (d, 3JH,H = 9.0

Hz, 2H, AQ) ppm; 13C NMR (75 MHz, CDCl3, 25 °C): δ = 39.90,

117.93, 125.65, 126.14, 128.70, 135.32, 158.25, 161.30, 183.11

ppm; IR (neat): ν = 2933, 1652, 1583, 1505, 1470, 1416, 1348,

1291, 1233, 1139, 1019, 901, 852, 744, 719, 683, 626 ppm;

UV/Vis (CH2Cl2): λmax (ε) = 406 (17900), 349 (29300), 291 (sh,

23700), 236 nm (23500 mol-1dm3cm-1); HR-FT-MALDI-MS (3-HPA)

m/z: calcd for C24H31N6O2+: 435.2503; found 435.2496 (MH+).

2,2'-(2-(Dimethylamino)anthracene-9,10-

diylidene)dimalononitrile (25). The title compound was

prepared from 14 (150 mg, 0.597 mmol), following the general

method. The mixture was heated to reflux for 48 h. Yield 188

mg (91%), dark violet solid. Rf = 0.75 (SiO2; CH2Cl2); M.p. 345

°C (dec.) [lit[2] m.p. 318-320 °C]; 1H NMR (300 MHz, CDCl3, 25

°C): δ = 3.19 (s, 6H, NCH3), 6.86 (dd, 3JH,H = 9.0 Hz, 4JH,H = 2.0

Hz, 1H, AQ), 7.42 (d, 4JH,H = 2.0 Hz, 1H, AQ), 7.63–7.71 (m, 2H,

AQ), 8.13–8.28 (m, 3H, AQ) ppm; 13C NMR (75 MHz, CDCl3, 25 °C):

δ = 40.26, 82.40, 109.75, 113.24, 113.50, 113.82, 114.42,

114.63, 115.61, 127.19, 127.25, 129.58, 129.96, 131.12,

131.38, 132.00, 132.20, 151.88, 159.28, 161.80 ppm (1C

missing); IR (neat): ν = 2216, 1606, 1547, 1520, 1501, 1467,

1372, 1350, 1329, 1108, 1062, 870, 819, 779, 698, 657 cm-1;

UV/Vis (CH2Cl2): λmax (ε) = 553 (8200), 414 (13100), 349

(24500), 272 nm (sh, 20500 mol-1dm3cm-1); HR-FT-MALDI-MS (3-

HPA) m/z: calcd for C22H14N5+: 346.1087; found 346.1091 (MH+).

2,2'-(2,6-Bis(dimethylamino)anthracene-9,10-

diylidene)dimalononitrile (26). The title compound was

prepared from 15 (150 mg, 0.51 mmol), following the general

method. The mixture was heated to reflux for 72 h. Yield 131

mg (66%), dark solid. Rf = 0.65 (SiO2; CH2Cl2); M.p. 356 °C

(dec.) [lit[3] m.p. 337-338 °C]; 1H NMR (300 MHz, CDCl3, 25 °C):

δ = 3.17 (s, 12H, NCH3), 6.79 (dd, 3JH,H = 9.0 Hz, 4JH,H = 2.0 Hz,

2H, AQ), 7.48 (d, 4JH,H = 2.0 Hz, 2H, AQ), 8.08 (d, 3JH,H = 9.0

Hz, 2H, AQ) ppm; 13C NMR (75 MHz, CDCl3, 25 °C): δ = 40.23,

76.10, 109.86, 112.84, 115.00, 115.08, 115.65, 129.45, 132.92,

152.03, 161.04 ppm; IR (neat): ν = 2919, 2208, 1603, 1548,

1495, 1446, 1378, 1322, 1291, 1211, 1123, 1068, 929, 850, 809,

796, 740, 698 cm-1; UV/Vis (CH2Cl2): λmax (ε) = 588 (sh, 4400),

509 (25800), 413 (30800), 358 (19100), 268 nm (26900 mol-1dm3cm-

1); HR-FT-MALDI-MS (3-HPA) m/z: calcd for C24H19N6+: 391.1666;

found 391.1660 (MH+).

2,2'-(2-Iodoanthracene-9,10-diylidene)dimalononitrile (29).

The title compound was prepared from 18 (200 mg, 0.59 mmol),

following the general method (see main manuscript). The

mixture was heated to reflux for 72 h. Yield 152 mg (59%),

yellow solid. Rf = 0.88 (SiO2; CH2Cl2); M.p.286–287 °C; 1H

NMR (300 MHz, CDCl3, 25 °C): δ = 7.74–7.77 (m, 2H, AQ), 7.95

(d, 3JH,H = 9.0 Hz, 1H, AQ), 8.09 (dd, 3JH,H = 9.0 Hz, 4JH,H = 2.0

Hz, 1H, AQ), 8.21–8.26 (m, 2H, AQ), 8.56 (d, 4JH,H = 2.0 Hz, 1H,

AQ) ppm; 13C NMR (75 MHz, CDCl3, 25 °C): δ = 83.17, 83.93,

99.28, 112.51, 112.60, 2 × 112.78, 127.54, 127.51, 128.28,

129.23, 129.57, 129.81, 131.47, 132.58, 132.62, 136.12,

141.19, 158.27, 159.19 ppm; IR (neat): ν = 2225, 1716, 1581,

1548, 1465, 1324, 1240, 1180, 1103, 935, 826, 773, 692 cm-1;

UV/Vis (CH2Cl2): λmax (ε) = 350 (22700), 296 nm (sh, 27600

mol-1dm3cm-1); HR-EI-MS m/z: calcd for C20H7IN4+: 429.9711; found

429.9710 (M+).

2,2'-(2,6-Dibromoanthracene-9,10-diylidene)dimalononitrile

(30). The title compound was prepared from 19 (200 mg, 0.55

mmol), following the general method. The mixture was heated

to reflux for 72 h. Yield 154 mg (61%), brown solid. Rf =

0.67 (SiO2; CH2Cl2); M.p. 287–288 °C [lit[3] m.p. 291-293 °C];

1H NMR (300 MHz, CDCl3, 25 °C): δ = 8.08 (dd, 3JH,H = 9.0 Hz,

4JH,H = 2.0 Hz, 2H, AQ), 8.25 (d, 3JH,H = 9.0 Hz, 2H, AQ), 8.49

(d, 4JH,H = 2.0 Hz, 2H, AQ) ppm; 13C NMR (75 MHz, CDCl3, 25 °C):

δ = 85.34, 113.90, 113.97, 126.65, 129.87, 130.04, 130.97,

133.05, 135.62, 158.67 ppm; IR (neat): ν = 3334, 2210, 1635,

1552, 1464,1322, 1268, 1178, 1082, 937, 898, 832, 757, 700 cm-

1; UV/Vis (CH2Cl2): λmax (ε) = 358 (20000), 300 nm (31100 mol-

1dm3cm-1); EI-MS (70 eV) m/z: 464 (53), 463 (24), 462 (100),

460 (51), 383 (23), 381 (19), 302 (52), 275 (36), 198 (33);

HR-EI-MS m/z: calcd for C20H6Br2N4+: 459.8954; found 459.8955

(M+).

X-ray analysis:

All X-ray measurements were carried out on a Bruker Kappa CCD

diffractometer equipped with graphite monochromator (MoKα

radiation, λ = 0.71073 Å) and an Oxford Cryostream low-

temperature device. Unit cell dimensions were obtained by

least-squares refinement of all measured reflexions (HKL,

Scalepack).[4] All structures were solved by direct methods

(SIR97[5], SHELXL-97[6]). Non-hydrogen atoms were refined

anisotropically by full-matrix least-squares analysis.

Hydrogen positions have been calculated and included in the

final structure factor calculation. All ellipsoids in the

ORTEP[7] plots are at the 50% probability level. For compounds

11 and 17, only very thin, multilayered crystals covered with

smaller crystals in random orientation were available, leading

to random overlapping of reflexions and bad R-values.

Table S1. Summary of the X-ray crystal structure data

10 11 17 20 25 32

Formula C30H26N4 C26H26N4 C24H30N6O2 C22H17NO2 C22H13N5 C30H18ClN5

Crystal size [mm]

0.44×0.2×0.06

0.58×0.08× 0.006

0.24×0.2×0.04

0.41×0.1× 0.06

0.6×0.2× 0.06

0.36×0.32× 0.24

Mr 442.57 394.52 434.54 327.38 347.38 483.96

T [K] 203 202 223.2 203.2 223 203.2

Crystal syst. monoclinic orthorhombic monoclinic monoclinic monoclinic monoclinic

Spacegroup P21 Aba2 P21/c P21/c P21/n P21/n

a [Å] 6.4246(3) 31.253(8) 10.0964(7) 12.7099(10) 10.4567(4) 9.9793(2)

b [Å] 8.3928(4) 23.711(6) 7.2737(5) 7.3839(2) 8.8982(4) 12.7394(3)

c [Å] 22.87(11) 6.940(2) 15.58(11) 34.6869(5) 19.3221(7) 18.3064(4)

α [°] - - - - - -

β [°] 93.101(2) - 94.957(3) 100.1825(4) 98.636(2) 91.579(13)

γ [°] - - - - - -

V[Å3] 1231.5(10) 5143(2) 1140.05(14) 3204.3(10) 1777.46(12) 2326.41(9)

Z 2 8 2 8 4 4

Unique refl. 3938 1971 2601 6302 3974 5276

Observed refl. (I>2σ)

3376 1560 1269 4099 2837 4180

parameters 411 271 145 587 296 397

R(obs) 0.059 0.144 0.166 0.058 0.056 0.051

Electrochemistry:

Figure S1. Representative cyclic voltammetry of TCAQs 24 (a), 25

(b), 26 (c) in the presence of ferrocene, and 27 (d) in CH2Cl2 +

0.1M n-Bu4NPF6 on a glassy carbon electrode (v = 0.1 V.s-1).

a)

b)

c)

d)

Optical spectroscopy:

Figure S2. UV/Vis spectra of the chromophores 10 and 11 in

(CH2Cl2).

Figure S3. Protonation/neutralization experiment for 31 in

CH2Cl2.

References:

[1] E. Winkelmann, W. Raether, Arzneim.-Forsch. 1979, 29, 1504–

1507.

[2] Y. Yamashita, T. Suzuki, T. Mukai, Nippon Kagaku Kaishi

1986, 5, 904-909.

[3] Y. Yamashita, T. Suzuki, T. Mukai, Nippon Kagaku Kaishi

1986, 3, 268-275.

[4] Z. Otwinowski, W. Minor, in Methods in Enzymology (Eds: C.

W. Carter, Jr., R. M. Sweet) Academic Press, New York,

1997, 276, 307–326.

[5] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.

Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G.

Polidori, R. Spagna, J. Appl. Cryst. 1999, 32, 115–119.

[6] G. M. Sheldrick, SHELXL97, Program for the Refinement of

Crystal Structures, University of Gottingen, Germany, 1997.

[7] C. K. Johnson, ORTEP–II, A Fortran Thermal–Ellipsoid Plot

Program, report ORNL-5138, Oak Ridge National Laboratory,

Oak Ridge, Tennessee, USA 1976.