SUPPORTING INFORMATION for. A Fused Donor - Acceptor System based on an Extended-Tetrathiafulvalene and a Ruthenium. Complex of Dipyridoquinoxaline

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1 UPPRTIG IFRMATI for A Fused Donor Acceptor ystem based on an ExtendedTetrathiafulvalene and a thenium Complex of Dipyridoquinoxaline Bertrand Chesneau, Marie Hardouin Lerouge and Piétrick Hudhomme* Laboratoire MLTECH Anjou, Université d'angers, CR UMR 6200, 2 Boulevard Lavoisier, Angers, France pietrick.hudhomme@univangers.fr List of contents of the upporting Information : Experimental procedures and spectroscopic data 2 1 H MR spectrum of qphen (7) : 4 1 H MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) 5 CY 1 H 1 H MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) 6 13 C MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) 7 19 F MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) 8 1 H MR spectrum of complex (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) 9 13 C MR spectrum of complex (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) F MR spectrum of complex (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) 11 MALDITF spectrum of complex (extttf dpq)(bpy) 2 (PF 6 ) 2 (1) Cyclic voltammogram of complex (extttf dpq)(bpy) 2 (PF 6 ) 2 (1) UVVisible spectra of complexes (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) and (qphen)(bpy) 2 (PF 6 ) 2 (8)

2 Experimental procedures and spectroscopic data : General procedures : The following chemicals were obtained commercially and were used without any purification. Thinlayer chromatography (TLC) was performed on aluminium sheets coated with neutral aluminium oxide 60 F 254. Column chromatography was carried out on silica gel 60A (4060 µm) or deactivated neutral alumina [deactivation by addition of H 2 (7g) in neutral aluminium oxide 50200µm (100g)]. 1 H (500 MHz), 13 C (125 MHz) and 19 F (470 MHz) MR spectra were recorded on spectrometer (Brucker Avance DRX 500). Chemical shifts are reported as δ values in ppm using CH 3 C as the reference. Infrared spectra were performed on a Perkin Elmer 841. Mass spectra were recorded on a MALDITF Brucker Biflex III. Electronic absorption spectra were recorded with a Lambda 19 IR model from PerkinElmer. 2,3Diphthalimido1,4naphthoquinone : To a solution of 2,3dichloro1,4naphthoquinone (4.54 g; 0.02 mol) in anhydrous acetonitrile (100 ml), potassium phthalidimide (15.54 g, mol), which was previously finely powdered and dried under vacuum, was added. The reaction mixture was refluxed for 3 h, then the hot solution was filtered. The precipitate was washed successively with cold acetonitrile (200 ml), water (200 ml) and methanol (200 ml). 2,3Diphthalimido1,4naphthoquinone was dried under vacuum at 50 C and isolated as a pale yellow powder (8.02 g) in 90% yield. 2,3Diamino1,4naphthoquinone 5: To a suspension of 2,3diphthalimido1,4naphthoquinone (2.24 g; 5 mmol) in water (150 ml) was added a 64% solution in water of hydrazine) (20 ml). The solution was stirred for 15 min at room temperature then heated at 6570 C for 3h. The reaction mixture was allowed to stand at room temperature. The precipitate was filtered, then washed with a large volume of water. Compound 5 was dried overnight under vacuum at 100 C and isolated as a purple powder (0.88 g) in 94% yield. The characterization data for compound 5 are in accordance of that reported by R. Díaz et al. 1 qphen 7: A solution of 2,3diamino1,4naphthoquinone 5 (188 mg; 1 mmol) and Phendione 6 (210 mg; 1 mmol) in glacial acetic acid (15 ml) was heated at 75 C for 1h. The reaction mixture was allowed to stand at room temperature. The precipitate was filtered, then washed with ethanol and diethyl ether. qphen 7 was isolated as a pale green powder (0.335 g) in 93% yield. The characterization data for compound 5 are in accordance of that reported by R. Díaz et al. 1 1 H MR (CDCl 3 ) δ : The spectrum could be performed despite the very low solubility of compound 7 in CDCl 3 13 C MR (CDCl 3 ) δ : The very low solubility of compound 7 did not allow the realization of the 13 C spectrum Complex (qphen)(bpy) 2 (PF 6 ) 2 8: A solution of qphen 7 (144.8 mg, 0.4 mmol) and (bpy) 2 Cl 2 (213 mg, 0.44 mmol) in anhydrous ethanol (20 ml) was heated under reflux under nitrogen atmosphere for 6 days. The reaction mixture was allowed to stand at room temperature, then a saturated aqueous solution of H 4 PF 6 (5 ml) was added. The precipitate was filtered, washed with water and diethyl ether. The precipitate was dissolved in acetonitrile and the solution was concentrated under vacuum. The residue was purified by chromatography on deactivated neutral alumina using acetonitrile as the eluent. Complex 8 was isolated after precipitation in a mixture of acetonitrile and diethylether as a ochre powder (223 mg) in 53 % yield. 1 H MR (CD 3 C) δ : 9.66 (dd, 1H, H4, 3 J = 8.5 Hz and 4 J = 1.5 Hz); 8.56 (dd, 1H, Hd or Hd, 3 J = 8 Hz and 4 J = 1.5 Hz); 8.52 (dd, 1H, Hd or Hd, 3 J = 8 Hz and 4 J = 1.5 Hz); 8.48 and 8.47 (2d, 1H, H5, 3 J = 6 Hz)*; 8.28 (dd, 1H, H2, 3 J = 5.5 Hz and 4 J = 1.5 Hz); 8.13 (dt, 1H, Hc or Hc, 3 J = 8 Hz and 4 J = 1.5 Hz); 8.06 and 8.05 (dd, 1H, 3 J = 6 Hz and 4 J = 3.5 Hz)*; 8,02 (dt, 1H, Hc or Hc, 3 J = 8 Hz and 4 J = 1.5 Hz); 7.96 (dd, 2H, H3, 3 J = 8 Hz and 3 J = 5.5 Hz); 7.85 (d, 1H, Ha or Ha, 3 J = 5.5 Hz); 7.70 (d, 1H, Ha or Ha, 3 J = 5.5 Hz); 7.48 (dt, 1H, Hb or Hb, 3 J = 6.5 Hz and 4 J = 1.5 Hz); 7.26 (dt, 1H, Hb or Hb, 3 J = 5.5 Hz and 4 J = 1.5 Hz). * Protons H5 and H5 appear as two doublets and these are consequently magnetically non equivalents. The same phenomenon is observed for protons H6 and H6. 13 C MR (CD 3 C) δ : 181.6; 158.1; 157.8; 155.9; 153.2; 153.1; 152.9; 152.8; 151.7; 146.2; 143.3; 138.9; 136.5; 135.1; 134.7; 130.8; 128.6; 128.5; 128.4; 125.3; F MR (CD 3 C) δ : 72,66, 74,16. IR (KBr, cm 1 ) : 1687 M Maldi/TF (dithranol; dichloromethane) m/z : 921 (35%, MPF 6 ) ; 845 (100%, MPF 6 76) ; 776 (38%, M2 PF 6 ) Complex (exttfdpq)(bpy) 2 (PF 6 ) 2 1: 1 Díaz, R.; Reyes,.; Francois, A.; Leiva, A. M.; Loeb, B. Tetrahedron Lett. 2001, 42,

3 To a solution of phosphonate 9 (416 mg, 1 mmol) in anhydrous THF (20 ml) under nitrogen atmosphere was added dropwise at 78 C nbuli 2.5 M in hexane (0.44 ml, 1.1 mmol). After stirring for 15 min at 78 C, compound 8 was added as a solid state and by small fractions (106.6 mg, 0.1 mmol). The reaction mixture was allowed to stand at room temperature under stirring for 24 h. We should note the color change of the solution from pale yellow to bordeaux around 15 C. After addition of methanol (20 ml), the solvent was concentrated under vacuum. The residue was purified by chromatography on deactivated neutral alumina using dichloromethane as the eluent to remove TTF(C 5 H 11 ) 4. The following elution using dichloromethane /methanol (95/5 V/V) as the mixture of eluents afforded complex 1 which was isolated in 43 % yield (70 mg) as a Bordeaux powder after precipitation using dichloromethane and petroleum ether. 1 H MR (CD 3 C) δ : 9.39 (d, 1H, H4, 3 J = 8 Hz); 8.59 (d, 1H, 3 J = 8Hz) and 8.56 (d, 1H, 3 J = 8Hz) (Ha and Ha ); 8.15 (m, 2H, H 2 + Hc or Hc ); 8.04 (dt, 3 J = 8 Hz, 4 J =1Hz, 2H, Hc or Hc ); 7.89 (d, 1H, H5, 3 J = 5.5 Hz); 7.85 (dd, 1H, H3, 3 J = 5 Hz, 3 J = 8 Hz,); 7.77 (d, 1H, H6, 3 J = 5.5 Hz); 7.50 (ddd, 1H, Hb or Hb, 3 J = 8 Hz, 3 J = 5 Hz, 4 J = 1Hz); 7.38 (m, 1H, Ha or Ha ); 7.34 (ddd, 1H, Hb or Hb, 3 J = 8 Hz, 3 J = 5 Hz, 4 J = 1Hz); 7.01 (m, 1H, Ha or Ha ); 2.77 (t, 2H, CH 2 CH 2, 3 J = 7.5 Hz); 2.72 (t, 2H, CH 2 CH 2, 3 J = 7.5 Hz); 1.45 (m, 4H); (m, 8H); 0.77 (t, 3H, CH 2 CH 3, 3 J = 7.5 Hz); 0.59 (t, 3H, CH 2 CH 3, 3 J =7,5 Hz). 13 C MR (CD 3 C) δ : 158.2; 158.1; 153.6; 153.0; 152.9; 149.0; 147.1; 146.6; 139.0; 138.9; 135.1; 134.3; 131.9; 131.6; 130.6; 128.7; 128.6; 127.8; 127.7; 126.6; 126.4; 125.4; 119.0; 118.6; 37.0; 36.5; 31.1; 31.0; 30.1; 30.0; 22.8; 22.6; 14.2; F MR (CD 3 C) δ : 72,64, 74,14 M Maldi/TF (dithranol, dichloromethane) m/z : 1648 (M +. ) UVVisible (CH 2 Cl 2 ) λ (ε) : 452 nm (40 800); 606 nm (19 600) 1 H MR spectrum of qphen (7) : 3

4 (CDCl 3, 20 C) ppm (f1) (CDCl 3, 50 C) ppm (f1) H MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) : 4

5 H c H c' H b' Hd' H d H a' H b H 2 H a 2+ 2 PF 6 H 3 H 4 H 5 H 6 H 5 ' H 6 ' H H H 6 H a 5 4 H c H d H 2 H c H 3 H a H b H b H d ppm (t1) CY 1 H 1 H MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) : 5

6 H c H c' H b' Hd' H d H a' H b H 2 H a 2+ 2 PF 6 H 3 H 4 H 5 H 6 H 5 ' H 6 ' 13 C MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) : 6

7 2 +, 2 PF ppm F MR spectrum of complex (qphen)(bpy) 2 (PF 6 ) 2 (8) : 7

8 2 +, 2 PF ppm H MR spectrum of complex (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) : 8

9 H c' H b' Hd' H d H a' H c H b H 2 H a 2+ 2 PF 6 H 3 H 4 C 5 H 11 H 5 H 6 C 5 H 11 H 2 + H 4 H d + H d H c ou H c H c ou H c H 3 H 5 H 6 H a ou H a H b H ou H b b ou H b H a ou H a C MR spectrum of complex (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) : 9

10 C 5 H , 2 PF 6 C 5 H ppm (f1) ppm (f1)

11 19 F MR spectrum of complex (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) : C 5 H , 2 PF 6 C 5 H ppm MALDITF spectrum of complex (extttf dpq)(bpy) 2 (PF 6 ) 2 (1) : C 5 H , 2 PF 6 C 5 H 11 11

12 Cyclic voltammogram of complex (extttf dpq)(bpy)2(pf6)2 (1) : Cyclic voltammetry was performed in a threeelectrode cell equipped with a platinum working electrode and a platinum wire counterelectrode. A silver wire in Ag3 solution 102M served as reference electrode and its potential was checked against the ferricinium/ ferrocene couple (Fc+/Fc) before and after each experiment. The electrolytic media involved CH2Cl2 and CH3C (HPLC grade), and 0.1 M of tetrabutylammonium hexafluorophosphate (TBAHP puriss quality). All experiments were performed in a glove box containing dry, oxygenfree (< 1ppm) argon, at room temperature. Electrochemical experiments were carried out with a BILGIC P 150 potentiostat. Cyclic voltammogram of complex 1 was recorded in a CH2Cl2/CH3C (9:1) solution (5.104 M) using Bu4PF6 0.1 M as the supporting electrolyte, platinum wires as counter and working electrodes, Ag/Ag3 as reference electrode, can rate: 100 mv/s. 12

13 Redox potential values (vs Fc + /Fc) of complex 1 : E ox1 E ox2 E red1 E red2 E red3 E pa E pc E 1/ Deconvoluted cyclic voltammogram : C 5 H , 2 PF 6 C 5 H 11 Cyclic voltammogram of complex 1 in positive direction : Cyclic voltammogram of complex 1 in negative direction : 13

14 UVVisible spectra of complexes (exttf dpq)(bpy) 2 (PF 6 ) 2 (1) and (qphen)(bpy) 2 (PF 6 ) 2 (8) in CH 2 Cl 2 (10 5 M) : C 5 H , 2 PF 6 C 5 H 11 14