, 44 g, 106.50 mmol, 3 eq.) was slowly added to the 2-methylbutan-2-ol (100 mL) at 120°C. The mixture was stirred at 120 °C until Na (0) was completely dissolved. Then the temperature was decreased to 90 °C and the 2-thiophenecarbonitrile (8.52 g, 78.1 mmol, 2.2 eq.) was added in one portion, affording a brown coloration of the reaction mixture. Afterwards, a solution of diethyl succinate (6.18 g, 35.5 mmol, 1 eq.) was added dropwise and the mixture was stirred at 120 °C overnight. The solution turned progressively in dark purple. After cooling to room temperature, the mixture was poured onto dilute HCl (1N, 100 ml) and was stirred vigourously for 1h at 0°C, resulting in the precipitation of a deep purple solid, collected by filtration under vacuum. The solid was washed several times with methanol. The crude product was dried under vacuum to give a purple powder (5.75 g, yield 54%) and used without further purification. 1 H NMR MHz, a flame-dried 250 ml bicol, sodium metal, p.6
, The mixture was stirred at 100 °C for 1 h under argon atmosphere. Then, 1-Bromononane (2.89 g, 13.98 mmol, 3 eq.) was added dropwise and the reaction mixture was stirred at 100 °C for 36 h, monitored in TLC (Rf = 0.6, using 100% CHCl3 as eluent). When the reaction was complete, it was cooled to room temperature and 200 ml of CH2Cl2 was added. The mixture was washed with 4 x 100 ml of brine. The organic layer was dried over MgSO4, filtered and evaporated under reduced pressure. The crude material was purified by chromatography using silica gel with CHCl3 as eluent to afford 2 as a purple solid (1.80 g, yield 70%). 1 H NMR (500 MHz, vol.18, pp.18-24
,
, 2918 and 2848 (w, v (N-CH2)), 1655, 1593 (w, v(C=O)). HRMS (ASAP+) (m/z): calc. for C32H44N2O2S2
, After cooling, the solvent was evaporated and the resulting solid was re-taken in CH2Cl2/CH3OH (30/30 ml), filtered and washed with methanol several times to give 6 (104.82 mg, 61% yield) as a dark purple solid. 1 H NMR (500 MHz, CDCl3), pp.184-227
, 137.7mg) was dissolved in a freshly distilled solution mixture of CH2Cl2/Et3N (15/15 mL). Then, copper iodide (3.0 mg, 16.0 mol), TMSA (38.30 mg, 0.39 mmol) and PPh3 (8.22 mg, 30.0 mol) were added. The mixture was degazed with an argon stream for 30 min before adding Pd(OAc)2 (3.52 mg, 16.0 mol), The reaction mixture was stirred at room temperature overnight
, CH2)), 2140 (w, v C?CC, and 1556 (w, v(C=O)). MALDI-tof (dithranol) calc. for C50H64N2O3S4 (8) exact mass, (m/z) = 908.34, 7.13 (m, 4H), 3.97 (t, 4H, J = 7.8 Hz), 1.73 (m, 4H), 1.40 (m, 4H), vol.1
, After removal of the solvent, the crude product was retaken in CH2Cl2 /MeOH (50/50 ml), filtered and washed with methanol to afford 9 (308.5 mg, 0.403 mmol, yield 80 %) as a purple solid. 1 H NMR (400 MHz
, The reaction mixture was evaporated and methanol (100 mL) was added. The precipitate was filtered and washed with methanol then dried under vacuum to provide 11 as a purple solid. (697.88 mg, yield 70 %). 1 H NMR (500 MHz, CDCl3 pp
, 37 mmol) in freshly distilled CH2Cl2 (10 mL) and Et3N (10 mL) was added copper iodide (7.04 mg, 40 mol, 10 mol %), TMSA (103.0 L, 0.74 mmol, 2 eq.) and PPh3 (19.40 mg, 74.0 mol, 20 mol %). The solution was degazed for 15 min under argon and Pd(OAc)2 (8.30 mg, 37 mol, 10 mol %) was then added. The mixture was stirred at room temperature overnight
,
,
, 90(cm -1 ): v = 2922 and 2851 (w, v (N-CH2, C?CC, and 1556 (w, v(C=O)). HRMS (ASAP+) Calc. for C37H53N2O2S2Si (12) [M+H] + , (m/z) = 649.32, 13C NMR (500 MHz, CDCl3 pp, vol.133
, /10 mL), K2CO3 (66.33 mg, 0.48 mmol, 3 eq.) was added
, , p.500
, 2916 and 2849 (w, v (N-CH2)), 1657 and 1558 (w, v(C=O)). HRMS (ASAP+) (m/z): calc. for C34H45N2O2S2
, Synthesis of compounds 14, vol.50, p.16
, -diylbis(thiophene-5,2-diyl))bis(2,5-dinonyl-3-(thiophen-2-yl)-2,5-dihydropyrrolo, vol.6
, mg, 0.28 mmol), copper iodide (5.20 mg, 29.0 ol, 10 mol%) and PPh3 (15.20 mg, 58.0 ol, ol%% were added to a mixture solution of freshly distilled CH2Cl2/NEt3 (10/10mL). The solution was degazed with a argon stream for 15 min before adding Pd(OAc)2 (6.50 mg, 29.0 ol, mol%). The mixture was stirred at room temperature overnight
, as eluent). Then, the reaction mixture was evaporated under reduced pressure to yield a solid which was re-taken in a mixture of CH2Cl2/MeOH (10/40 mL). Finally, the solid was filtered and washed with methanol several times to obtain 15 as dark blue solid (157.80 mg, yield 50%). 1 H NMR (500 MHz, pp.3-8
, diyl))bis(3-(5-bromothiophen-2-yl)-2,5-dinonyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (15) In a 50 mL round bottom flask wrapped with aluminium foil, 15 (112.70 mg, 0.10 mmol) was dissolved in CH2Cl2 (20mL). NBS (44.49 mg, 0.25 mmol, 2.5 eq.) was added in a single portion. The mixture was stirred at room temperature for 8 hours and monitored in CCM
, Since the separation of those products was very difficult, the crude material was directly engaged in the next step. MALDI-tof (dithranol) calc. for C66H84Br2N4O4S4 (15) [M+H] + (m/z) = 1283.37 and measured [M+H] + (m/z) = 1287.35. Calc. for C66H85Br2N4O4S4 (15') [M+H] + (m/z) = 1204.46, measured [M+H] + (m/z) = 1206, 43. 6,6'-(ethyne-1,2-diylbis(thiophene-5,2-diyl))bis(2,5-dinonyl-3-(5-((trimethylsilyl)ethynyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (16, L3) In a flame-dried schlenk the crude material composed of 15 and 15' (100mg) was dissolved in a mixture solution of freshly distilled CH2Cl2/NEt3 (10/10mL), then copper iodide (1.52 mg, 8 mol), TMSA (19.64 mg, 0.20 mmol) and PPh3 (4.20 mg, 16.0 ol eee added. The solutio as degazed ith an argon stream for 15 min before adding Pd(OAc)2 (1.80 mg, 8.0 ol. The itue as stied at ooo teepeeatue ooeight, /60 as eluent). Then, the reaction mixture was evaporated under reduced pressure and the crude product was re-taken in methanol (50 mL), vol.2, p.5
, 250 ml flame-dried schlenk 1 (317.4 mg, 1.06 mmol), K2CO3 (439.47 mg, 3.18 mmol, 3eq.) and 18 Crown 6 (cat. 5 mg) were added in distilled DMF, p.40
, , vol.7
, Synthesis of compounds 22, 23, 25. 2,5-bis(9-bromononyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (22) In a 250 ml flame-dried schlenk 1 (1.0 g, 3.33 mmol), K2CO3 (1.38 g, 9.99 mmol, 3 eq.), 18Crown6 (cat. 5 mg) and 1,9-dibromononane (4.06 g, 16.65 mmol, 5 eq.) were added in 80 ml of distilled N, N-dimethylformamide (DMF) under argon atmosphere. The mixture was heated at 60 °C for 18 h, monitored in TLC (Rf = 0.60, using CH2Cl2/pentane 60/40 as eluent). The reaction was cooled to room temperature, CH2Cl2 was added and the mixture was extracted with 4 x 100 ml of brine. The organic layer was dried over MgSO4, ] + (m/z) = 813.64. T m.p (°C) = 152, vol.55
, CHCl3/pentane (60/40) as eluent to afford 22 as a purple solid (1.18 g, yield 50%)
, IR (cm -1 ): v = 3100, 3082 (v, C-H aromatic), 2926 and 2851 (w, v (N-CH2)), 1658 and 1558 (w, v(C=O)), 721 (v, C-Br alcane). HRMS (ASAP+) Calc, vol.3
,
, , pp.8-66
, IR (cm -1 ): v = 3090 (v, C-H aromatic), 2924 and 2852 (w, v (N-CH2)), 1659 and 1558 (w, v(C=O)). HRMS (ASAP+) Calc, 13 C NMR (500 MHz, CDCl3, pp.161-165
, (triisopropylsilyl)ethynyl)thiophen-2-yl)-2,5-dihydropyrrolo, vol.2, pp.6-11
, 21 mmol) was dissolved in a mixture solution of freshly distilled CH2Cl2/NEt3 (10/10mL). Then, copper iodide (4.09 mg, 21.51 µmol, 10 mol %), triisopropylsilylacetylene (95.74 mg, 0.52 mmol, 2.5 eq.) and PPh3 (11.01 mg, 42.0 µmol, 20 mol %) were added. The solution was degazed with an argon stream for 15 min before adding Pd(OAc)2 (4.82 mg, 21.51 µmol, 10 mol %). The reaction mixture was stirred at room temperature overnight
, 51.48; 42.24; 29.99; 29.74; 29.36; 29.11; 28.83; 26.81; 26.68; 10.59; 11.30. IR (cm -1 ): v = 2924 and 2864 (w, v (N-CH2)), C?CC, 089 (w, v(C-N)), 1658 and 1551 (w, v(C=O)). MALDI-tof (dithranol) Calc
, Then, copper iodide (2.19 mg, 11.5 µmol, 10 mol %), triisopropylsilylacetylene (34.19 mg, 0.144 mmol, 2.5 eq.) and PPh3 (6.03 mg, 23.0 µmol, 20 mol %) were added. The solution was degazed with an argon stream for 15 min before adding Pd(OAc)2 (2.58 mg, 11.5 µmol, 10 mol %). The mixture was stirred at room temperature overnight, monitored in TLC (Rf = 0.70, using AcOEt/pentane 50/50 as eluent). The solution was evaporated under reduced pressure and the crude product was purified by column chromatography on silica gel using AcOEt/Pentane (40/60) as eluent, 115 mmol) was dissolved in a mixture solution of freshly distilled CH2Cl2/NEt3 (10/10mL)
,
, (m, 4H), 1.74-1.68 (m, 4H) 1.42-1.36 (m, 8H), 1.34-1.27 (m, 18H), 1.11 (s, 48H). 13 C NMR (500 MHz
, Purification by column chromatography on silica gel with AcOEt/Pentane (60/40) as eluent give the product as a dark blue solid (43.0 mg, yield 70%). 1 H NMR (500 MHz, A (29.67 mg, 0.126 mmol)
,
, 73, 30.93, 30.81, 29.22, 29.03. IR (cm -1 ): v = 2927 and 2862 (w, v (N-CH2)), 2225 (w, v (C?N, C?CC, and 1603 (w, v(C=O)). MALDI-tof (dithranol) calc. for C86H104N10O4S2Si2 (28) exact mass, (m/z) = 1460.72; measured exact mass (m/z) = 1461, 1.87 (m, 4H), 1.68 (m, 4H), 1.37 (m, 4H), 1.31-1.26 (m, 17H), 1.11 (s, 48H). 13 C NMR (600 MHz, vol.3
, Purification by column chromatography on silica gel with AcOEt/Pentane (40/60) as eluent give the product as a dark blue solid (52.07 mg, yield 75%). 1 H NMR (500 MHz, B (44.12 mg, 0.121 mmol)
,
, (m, 4H), 1.35-1.23 (m, 42H), 1.11 (s, 48H), 0.86 (t, 6H, J = 6.5 Hz). 13 C NMR (600 MHz
, 11-pentakis(hexyloxy)triphenylen-2-yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)nonyl)-3,6-bis(5-((triisopropylsilyl)ethynyl)thiophen-2-yl)-2,5-dihydropyrrolo, vol.2, p.4
, 500 MHz, CDCl3) pp: 8.78 (d, 2H, J = 4.2 Hz), 8.06 (s, 2H), 7.79 (m, 10H), vol.7
, IR (cm -1 ): v = 2926 and 2858 (w, v (N-CH2)), 2137 (w, v C?CC, and 1616 (w, v(C=O)), 1259 and 1169 (w, v(C-O)). MALDI-tof (dithranol) calc. for C156H230N8O14S2Si2 (30) exact mass, .85 (m, 20H), 1.69-1.63 (m, 6H), 1.59-1.52 (m, 20H), 1.40-1.33 (m, 47H), 1.27-1.23 (m, 17H), 1, 07 (m, 48H), 0.90 (m, 32H). 13 C NMR (600 Hz, CDCl3, pp.160-162
, (triisopropylsilyl)ethynyl)thiophen-2-yl)pyrrolo, pp.4-7
, bis(methylene))bis(oxy))bis([1'',1'''-biphenyl]-4-carbonitrile) (28a)
, Pentane (60/40) as eluent give the product as a dark blue solid (20.64 mg, yield 40 %). 1 H NMR (500 MHz, As byproduct, compound 31a was purified by column chromatography on silica gel with AcOEt, vol.3
,
, , p.2095
, (triisopropylsilyl)ethynyl)thiophen-2-yl)pyrrolo, Calc. for C70H93N9O3S2Si2 (28a) [M+H] + (m/z) = 1227.64 ; measured [M+H] + (m/z) = 1228.76. T m.p (°C) = 95, pp.4-7
, As byproduct, compound 30a was purified by column chromatography on silica gel with AcOEt/Pentane (30/70) as eluent give the product as a dark blue solid (20.79 mg, yield 38 %). 1 H NMR (500 MHz, CDCl3 pp, vol.7
, N?N)), 1693 (w, v(C=O)), 1624 (w, v(C=O)), 1249 (w, v(C-O)). MALDI-tof (dithranol) Calc, 1.87 (m, 2H), 1.77 (m, 2H),1.69 (m, 4H), 1.45 (m, 4H), 1.33-1.27 (m, 28H), 1.11 (m, 48H), 0.86 (m, 3H). 13 C NMR (600 MHz, CDCl3 pp, vol.17, p.11
, 99 (m, 4H), 1.96-1.85 (m, 15H), 1.59-1.52 (m, 24H), 1.40-1.33 (m, 40H), As byproduct, compound 30a was purified by column chromatography on silica gel with AcOEt/Pentane (30/70) as eluent give the product as a dark blue solid (13.25 mg, yield 20 %). 1 H NMR (500 MHz, CDCl3) pp: 8.79 (dd, 2H), 8.05 (s, 1H), 7.79 (m, 5H), 7.64 (s, 1H), 7.29 (d, 2H), vol.5, pp.1261-1170
, (triisopropylsilyl)ethynyl)thiophen-2-yl)pyrrolo[3,4-c]pyrrole-2,5(1H,4H)-diyl)bis(nonane-9,1-diyl))bis(1H-1,2,3-triazole-1,4-diyl))bis(methylene) bis, pp.4-7
, CuSO4 (2.15 mg, 13.48 µmol) and sodium ascorbate (10.68 mg, 53.92 µmol). Purification by column chromatography on silica gel with AcOEt/Pentane (80/20) as eluent give the product as a dark blue solid (m = 80.26 mg, yield 69%). 1 H NMR (500 MHz, G = With 27 (67 mg, 67.40 µmol), D (76.6 mg, 0.202 mmol)
, 45 µmol) in degazed and distilled mixture solution of CH2Cl2/Et3N (10/5, v/v) was added CuI (1.58 mg, 8.34 µmol, 10 mol %), triisopropylsilylacetylene (38.05 mg, 0.208 mmol, 2.5 eq.) and PPh3 (2.18 mg, 16.68 µmol, 20 mol %). The mixture was degazed under argon atmosphere for 15 min before to add Pd(OAc)2 (1.87 mg, 8.34 µmol, 10 mol %). The mixture was stirred at room temperature overnight. The solution was evaporated under, 3.94 (m, 4H), 2.07 (m, 2H), 1.88-1.84 (m, 4H), 1.71-1.65 (m, 8H), 1.59-1.54 (m, 6H), 1.36 (d, 6H), 1.30-1.20 (m, 58H), 1.11 (m, 48H), 0.83 (m, 14H). 13 C NMR (600 MHz, CDCl3 (ppm): 175.90, 171, vol.34, p.2139
,
, 13 C NMR (500 MHz, CDCl3) (ppm): 161.16, 159.90, 145.30, 3.97 (t, 4H, J = 6.5 Hz), 1.79-1.74 (m, 4H), 1.73-1.68 (m, 4H), 1.46-1.39 (m, 8H) 1.36-1.31 (m, 12H), vol.1, p.2139
, 1-diyl))bis(4'-(octyloxy)-[1,1'-biphenyl]-4-carboxamide) (34) To a mixture of the crude product 33 (62 mg) and [1,1'-Biphenyl]-4-carboxylic acid, 4'-(octyloxy)(85.52 mg, 0.260 mmol) in a distilled mixture of CH2Cl2/Et3N (10/2, v/v) was added HOBT (41 mg, 0.267 mmol), DCC (54 mg, 0.267 mmol).The reaction mixture was stirred at room temperature for 48h. The solution was evaporated under vacuum and the crude product was purified by column chromatography using a mixture of 60/40 AcOEt/pentane as eluent, triisopropylsilyl)ethynyl)thiophen-2-yl)pyrrolo[3,4-c]pyrrole-2,5(1H,4H)-diyl)bis(nonane-9, pp.4-7
, 1.48-1.42 (m, 8H), 1.38-1.26 (m, 40H), 1.11 (m, 48H), 0.86 (m, 6H). 13 C NMR (500 MHz, 3.97 (t, 4H, J = 6.6 Hz), 3.43 (m, 4H), 1.80-1.76 (m, 4H), 1.73-1.67 (m, 4H), pp.2923-2854
, General procedure for platinium (II) metallo-oligomers formation In a 10 ml flame-dried schlenk, the diethynyl ligand Ln (1 eq.), copper iodide (10 mol %) and transdichlorobis(triethylphosphine)platinum(II) [PtCl2(Pn-Bu3)2] (1 eq.) were added, those solids were degassed with three cycles of argon/vacuum. Then, there were dissolved in a solvent mixture of freshly distilled and degazed CH2Cl2/NEt3 4/2 (v/v). Finally the tetra-n-butylammonium fluoride (TBAF) (2 eq., 1 mol.L -1 solution in THF) was added. The reaction was stirred at room temperature for 24 hours under argon atmosphere. The reaction was monitored in phosphorus NMR. The solution was evaporated under reduced pressure. The crude material was purified by a cristallisation in CH2Cl2/MeOH (50/50 v/v). The precipitate was isolated as a dark blue colored solid after a filtration and washings with methanol. Finally, the platinium (II) polyyne polymers Pn were quickly passing throught a biobead column to remove monomers residues impurities. Convergent synthesis Schéma 66 : Synthesis of compounds A and B. '-prop-2-ynyloxy-biphenyl-4-carbonitrile (A) In a 25 ml rom-bottomed flask, 4?-hydroxybiphenyl-4-carbonitrile (400 mg, 2.05 mmol) and K2CO3 (566.33 mg, 4.09 mmol, 2 eq.) were added with 10 mL of acetone, The reaction mixture was stirred at room temperature for 48h. The crude solution was evaporated under reduced pressure and the crude product was first purified by column chromatography using AcOEt/MeOH (97/3) as eluent. 37 with impureties were then passed through a biobead chromatography to give 37 as a dark purple solid (15 mg, 27% over two steps). 1 H NMR (500 MHz CDCl3 pp: .. d, vol.1, pp.2926-2863
, 4-carboxylic acid, 4'-(octyloxy)-, 3-etyn-1-yl ester (B) In a 25 mL rom-bottomed flask, [1,1'-Biphenyl]-4-carboxylic acid, 4'-(octyloxy) (400.0 mg, 1.22 mmol), DCC (505.50 mg, 2.45 mmol, 2 eq.) and DMAP (30.0 mg, 0.244 mmol, 20 mol %) were added with 10 mL of distilled CH2Cl2. Then propargyl alcohol (137.40 mg, 2.45 mmol, 2 eq.) was added dropwise. The mixture was stirred at room temperature for 24h. The crude product was extracted with CH2Cl2 and brine (2 x 100 mL), organic layers were dried over MgSO4, filtered and evaporated under reduced pressure. The product was purified by column chromatography on silica gel using AcOEt/Pentane (10/90) as eluent to provide B as a white solid
, IR (cm -1 ): v = 3253 (w,v(C-H)), 2923 and 2852 (w, v (O-CH2)), 2118 (w, C?CC, 1722 (w, v (C=O)), 1282 (w, v(C-O) aromatic ether). HRMS (ASAP+) Calc
, 11-penta-hexyloxytriphenylene 186 are synthesized according to literature. 2-mono-hydroxy-3,6,7,10,11-penta-hexyloxy-triphenylene In a 50 mL schlenk flask was added under argon atmosphere 2-mono-hydroxy-3, vol.6
, 10 mmol), K2CO3 (27.63 mg, 0.199 mmol, 2 eq.) in distilled DMF (8 mL). Then, propargylbromide (23.78 mg, 0.199 mmol, 2 eq
, The crude product was purified by column chromatography on silica gel using AcOEt/Pentane (1/9) as eluent. Compound C was obtain as an off-white solid (m = 57.16 mg, yield 73 %). 1 H NMR (400 MHz, CDCl3
, Chem. Eur. J, vol.22, p.8113, 2016.
, Tetrahedron Letters, vol.56, p.700, 2015.
, Synthesis of compounds diAA-1 et diAA-2, Schéma, vol.68
,
, 71 mmol, 765.44 mg, 1.3 eq.) were added in a 50 ml rom-bottomed flask with 30 ml of CH2Cl2 and stirred for 30 min at 0°C. Then, L-Alanine, ethyl ester, hydrochloride (437.78 mg, 2.85 mmol) with5 mL of NEt3 in 10 mL of CH2Cl2 were added. Reaction was stirred at room temperature for 48h.The mixture was extracted with CH2Cl2 and brine (2 x 100 mL), then organic layers were dried over MgSO4, filtered and evaporated under reduced pressure. The crude product was purified by column chromatography on silica gel using AcOEt/Pentane (6/4) as eluent, .85 mmol, 500 mg), HOBt (3.71 mmol, 568.18 mg, 1.3 eq.) and DCC, p.400
, 62 (s, 1H), vol.5, p.6
, tert-butoxycarbonyl)amino)acetamido)propanoic acid (diAA-2) mixture was filtered and washed with CH2Cl2. After evaporation of solvants, the crude was filtered and used without futher purification
, -butylnonanamido)acetamido)propanoate were added in a 50 mL rom-bottomed flask with a mixture solution of H2O/MeOH (10/40 mL) at 0°C. Then the reaction was stirred at room temperature for 4h. AcOEt (100 mL) was over MgSO4, filtered and evaporated under reduced pressure. The final product was obtain without futher purification as a white solid, Monohydrate lithium hydroxide (excess) and the crude ethyl2
, eq.) and DMAP (20 mol %) were added with 10 mL of distilled CH2Cl2. Then propargyl alcohol (2 eq.) was added dropwise. The mixture was stirred at room temperature for 24h. The crude product was extracted with CH2Cl2 and brine (2 x 100 mL), organic layers were dried over MgSO4, filtered and evaporated under reduced pressure. The product was purified by column chromatography on silica gel using AcOEt/Pentane (30/70) as eluent to provide diAA-3 as a white solid, butyloctanamido)acetamido)propanoic acid, DCC
, 2924 and 2853 (w, v (N-CH2)), 1739 (w, v (C=O), ester), 1650 (w, v (C=O) amide), 1203 and 1153 (w, v(C-O) ester). HRMS (ESI+) Calc, IR (cm -1 ): v = 3291
, Annexe A : Voltamétrie cyclique
, Les mesures en voltamétrie cyclique ont été réalisées par Muriel Durandetti du laboratoire COBRA à Rouen. Les analyses sont réalisées sur film par drop casting sur embout de platine en utilisat l'aaatooitile ooe solaat daas la ellule. L'hexafluorophosphate de tétrabutylammonium (NBu4PF6) est ajouté à la solution
, Une électrode de référence (possédant un potentiel fixe), au calomel saturée
, Composés du chapitre 2 Figure 184 : Courbe du potentiel d'odo-réduction de P1
, Etude des popitts d'''issioo des ligads et tallo-polymères Chapitre
, Ces aaalses peeettet de oaite la loogueu d'oode aaiale d'eeeitatioo et d'''issio. Cooe dtaill daas le hapitre 1 (III.4), dans la photoluminescence, on distingue deux processus. Le premier est la fluorescence, elle traduit l'aasooptio d'u photo d'u tat fodaaetal S0 vers un état excité singulet S1
, Le deuxième est la phosphorescence, où la taasitioo d'u tat S1 vers un état triplet T1 se produit
, Cette transition S1?T1 suii de l'''issioo du photoo à S0 est plus lete à effetuee de l'oode de 10 -3 à quelques secondes contre 10 -9 à 10 -6 s pour la fluorescence)
, La Figure 208b dit le phooe de phosphooesseee, s'il a lieu, aaee la atio d'u tat tiplet T1. Sur le schéma, Lors de la transition vers un état excité singulet S1 (flèches bleus), une relaxation vibrationnelle rapide vers le niveau v = 0 de S1 (non radiative) se produit (flèches noires), suivit de la fluorescence (flèches vertes), La Figure 208a psete la supeepositioo gggale d'u speete d'aasooptioo et d'issio aaee la représentation des différentes transitions vibroniques associées aux phénomènes d'aasooptioo et de fluooesseee
, soit pour un métallo-polymère portant un ligand accepteur (212b) 79 . Figure 212 : Mécanisme général du transfert d'egie pset das a. u tallo-polymère portant un ligand donneur et b.un métallo-polymère, possibles soit pour un métallo-polymère portant un ligand donneur (212a)
, Daas ote as, l'iflueee du platie est duite, dfaaooisaat le oiseeet itee-système (ISC) peeettat le passage es u tat tiplet
, De plus, les valeurs de ? obtenus, entre 0,71 et 2,45 ns sont en accord avec une décroissance adiatie d'u tat sigulet eeeit es l''tat fodaaetal
, La Figure 213 présente les peiees speetes d'aasooptioo, d'eeeitatio et d'''issio alisss pou P5 et P7 et mesuré sur film mince. Pour P6, uiueeeet les speetes d'aasooptio et d'eeeitatio oot pu te esus, le siggal d'''issioo 'a pas pu tte dteet à la logueu d'oode d'eeeitatioo utilisse. Métallo-polymère possédant un fort ligand conjugué donneur Métallo-polymère, Les analyses ont pu être effectuées pour les composés P5, P6 et P7