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Electronic Supplementary Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of oligoalkylthiophene 1,3,4-oxadiazole derivatives Aleksandra Kurowska1,

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  • Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of

    oligoalkylthiophene 1,3,4-oxadiazole derivatives

    Aleksandra Kurowska 1 , Pawel Zassowski

    1 , Anastasia S. Kostyuchenko

    2,3 , Tatyana Yu. Zheleznova2,

    Kseniya V. Andryukhova 4 , Alexander S. Fisyuk

    2,4 , Adam Pron

    5 , Wojciech Domagala

    1, *

    1 Department of Physical Chemistry and Technology of Polymers, Silesian University of Technology, Marcina Strzody 9, 44-100

    Gliwice, Poland 2 Laboratory of New Organic Materials, Omsk State Technical University, Mira ave. 11, Omsk 644050, Russian Federation

    3 RUDN University, 6 Miklukho-Maklaya st, Moscow 117198, Russian Federation

    4 Department of Organic Chemistry, Omsk F. M. Dostoevsky State University, Mira ave. 55A, Omsk 644077, Russian Federation

    5 Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

    Electronic Supplementary Information

    Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is © the Owner Societies 2017

  • page S2 of 33

    Synthetic procedures with instrumental and analytical product validation data

    General Information

    The IR spectra were recorded on an Infralum FT-801 spectrometer in KBr pellets for solids, or in thin

    films for liquid compounds. The 1H and 13C NMR spectra were obtained in CDCl3 or DMSO with TMS as an

    internal standard, using a Bruker DRX 400 spectrometer (400 and 100 MHz, respectively). The elemental

    analyses were carried out on a Carlo Erba 1106 CHN analyzer. The melting points were determined on a

    Kofler bench. The reaction course and purity of the products were checked by thin-layer chromatography

    on Sorbfil UV-254 plates which were visualized with UV light. All chemicals were of analytical grade and

    purchased from Sigma-Aldrich Chemical Co. Compound 7a,1,2 7b,2 6,3 4,4 terthiophene,5,6 1,4-di(2H-tetrazol-

    5-yl)benzene,7 7c,8 3,9 were prepared according to known procedures.

    Experimental and analytical data

    Ethyl 3-decyl-5'-dodecanoyl-[2,2'-bithiophene]-5-carboxylate (8)

    A mixture of lauric acid 1.74 g (8.7 mmol), 1.25 ml (17.4 mmol) thionyl

    chloride and one drop of DMF as a catalyst was stirred for 2.5 h at 45-50 0C.

    The excess of thionyl chloride was evaporated under reduced pressure. The

    obtained undecanoyl chloride and ethyl 3-decyl-[2,2'-bithiophene]-5-carboxylate 7a (7.9 mmol) were

    dissolved in 15 ml anhydrous chlorobenzene. The solution was cooled in an ice bath and SnCl4 (0.95 ml,

    7.9 mmol) was then added with vigorous stirring. The reaction mixture was stirred for 1 h under cooling

    and for additional 4.5 h at room temperature. Then 5 ml 2M HCl was added slowly. The organic layer was

    washed with aqueous NaHCO3 and water then dried over Na2SO4. The solvent was removed on a vacuum

    evaporator and the product purified by column chromatography (silica gel, hexane/EtOAc, 20/1).

    Yield: 2.4 g (62%); yellow solid; Rf = 0.33 (silica gel, hexane/EtOAc, 20/1). M.p.=33-360С.

    IR (KBr). ν сm-1: 1664 (С=О), 1712 (CO2Et).

    1H NMR (400 MHz, CDCl3, δ, ppm): δ = 0.88 (6H, t., 3J=6.8 Hz, 2СH3); 1.26-1.37 (30H, m., 15СН2); 1.38 (3H, t.,

    3J=7.1 Hz, ОСН2CH3); 1.61-1.69 (2H, m., ThCH2CH2C8H17); 1.72-1.79 (2H, m., 2-ThСОCH2CH2C9H19); 2.78 (2H,

    t., 3J=7.1 Hz, Th-CH2C9H19); 2.88 (2H, t., 3J=7.4 Hz, Th-СОCH2C10H21); 4.36 (2H, q.,

    3J=7.2 Hz, OCH2CH3); 7.20

    (1H, d., 3J=3.9 Hz, Th-3′-H); 7.63(1H, s., Th-4-H); 7.64 (1H, d., 3J=3.9 Hz, Th-4′-H).

    13C NMR (100 MHz, δ, ppm): 14.07 (C9H18СН3, COC10H20CH3), 14.40 (COCH2СН3), 22.70, 24.89, 29.33, 29.35,

    29.39, 29.43, 29.45, 29.49, 29.51, 29.56, 29.60, 29.64, 30.30, 31.91, 31.93, 39.26 (19СН2), 61.36 (CO-

    СН2CH3), 127.31 (3′-Th), 131.88 (4-Th), 132.67 (5-Th), 135.94 (4′-Th), 136.54 (2-Th), 141.70 (2’-Th), 143.00

    (3-Th), 144.44 (5′-Th), 161.94 (CO2C2H5), 193.31 (С=O).

    Elemental analysis. Calculated for C33H52O3S2: С, 70.73%; Н, 9.39%. found: С 70.66%, Н 9.34%.

  • page S3 of 33

    3-Decyl-5'-dodecanoyl-[2,2'-bithiophene]-5-carboxylic acid (9)

    A solution of ethyl 3-decyl-5'-dodecanoyl-[2,2'-bithiophene]-5-carboxylate 8

    2.81 g (5.0 mmol) and potassium hydroxide 1.12 g, (20.0 mmol) in 6 mL ethanol

    was refluxed for 4 h. Ethanol was removed under reduced pressure, 8 ml of water

    was added to the residue and the mixture was acidified with dilute 2 N hydrochloric acid. The precipitate

    was separated and recrystallized from methanol.

    Yield: 2.2 g (82%); yellow solid. M.p.=175-1770С.

    IR (KBr). ν сm-1: 1668 (С=О), 2500-3460 (O-Н).

    1H NMR (400 MHz, CDCl3 δ, ppm): δ = 0.83-0.89 (6H, m., 2СH3); 1.18-1.33 (30H, m., 15СН2); 1.51 (2H, s.,

    ThCH2CH2C8H17); 1.68-1.71 (2H, m., 2-ThСОCH2CH2C9H19); 2.59 (2H, s., Th-CH2C9H19); 2.78-2.81 (2H, m., Th-

    СОCH2C10H21); 7.03 (1H, s., Th-3′-H); 7.46(1H, s., Th-4-H); 7.52 (1H, s., Th-4’-H).

    13C NMR (100 MHz, δ, ppm): 14.13 (C9H18СН3, COC10H20CH3), 22.71, 24.73, 29.39, 29.45, 29.53, 29.59, 29.70,

    30.16, 31.94, 39.12 (19СН2); 126.89 (3′-Th); 131.75 (4′-Th); 133.90 (5-Th); 135.93 (2-Th); 136.54 (4-Th);

    141.64 (2’-Th); 143.10 (5′-Th), 143.96 (3-Th), 166.95 (CO2Н), 193.09 (С=O).

    Elemental analysis. Calculated for C31H48O3S2: С, 69.81%; Н, 9.01 %. found: С, 69.88%; Н, 9.08 %.

    1-(3'-Decyl-[2,2'-bithiophen]-5-yl)dodecan-1-one (10)

    A mixture of acid 9 (2.10 g, 3.9 mmol), 5.6 mL quinoline and (0.12 g, 2.0 mmol) copper

    was stirred for 1 h at 225 0C. 7 ml of 15% hydrochloric acid was added to the residue

    and the mixture was stirred for 30 min at room temperature. Then product was

    extracted with CH2Cl2 (10ml×3). The combined organic extract was washed with water (30 mL), dried

    (Na2SO4) and concentrated. The product purified by column chromatography (hexane/EtOAc, 20/1) and

    crystallized from ethanol.

    Yield: 1.2 g (62%); yellow solid. M.p.=49-52 0С.

    IR (KBr). ν сm-1: 1649 (С=О).

    1H NMR (400 MHz, CDCl3, δ, ppm): δ = 0.88 (6H, t., 3J=6.8 Hz, 2СH3); 1.26-1.38 (30H, m., 15СН2); 1.59-1.68

    (2H, m, ThCH2CH2C8H17); 1.72-1.79 (2H, m., 2-ThСОCH2CH2C9H19); 2.80 (2H, t., 3J=7.8 Hz, Th-CH2C9H19); 2.87

    (2H, t., 3J=7.4 Hz, Th-СОCH2C10H21); 6.95 (1H, d., 3J=5.1 Hz, Th-4′-H); 7.12 (1H, d., 3J=4.0 Hz, Th-3-H); 7.23

    (1H, d., 3J=5.1 Hz, Th-5′-H); 7.63 (1H, d., 3J=4.0 Hz, Th-4-H).

    13C NMR (100 MHz, δ, ppm): 14.13 (2CH3); 22.70, 24.99, 29.34, 29.35, 29.40, 29.45, 29.46, 29.48, 29.51,

    29.52, 29.59, 29.61, 29.63, 29.64, 30.50, 31.91, 31.92, 39.15 (19СН2); 125.13 (3-Th); 126.13 (5’-Th);

    129.91(4’-Th); 130.48 (4-Th); 132.05 (2-Th); 141.39 (2’-Th); 143.06 (5-Th); 144.67(3’-Th); 193.42 (С=O).

    Elemental analysis. Calculated for C30H48OS2: С, 73.84%; Н, 9.99%. found: С 73.71%, Н 9.90%.

  • page S4 of 33

    2-(Chloro(3'-decyl-[2,2'-bithiophen]-5-yl)methylene)dodecanal (11)

    To DMF (8 ml) at 00C was added POCl3 (0.75 ml, 8.2 mmol) and the mixture was

    stirred for 30 min at the same temperature. In the next step a solution of ketone

    I9 (1.9 mmol) in DMF (2 ml) was added dropwise. The reaction mixture was

    heated at 60 - 650C for 5 h. Then the solution was poured on a crushed ice (20 g) in water (70 ml) and

    extracted with EtOAc (3 × 10 ml). The combined organic layers were washed with saturated solution of

    NaOAc and dried with anhydrous Na2SO4. The solvent was evaporated under reduced pressure. The crude

    product was purified by column chromatography on silica gel.

    Yield: 0.61 g (60%); yellow oil. Rf=0.58, 0.60 (hexane/EtOAc, 20/1)

    IR (KBr). ν сm-1: 1671 (С=О). Z/E=19/81

    1H NMR (400 MHz, CDCl3, δ, ppm): E-(11): 0.86-0.90 (6H, m., 2СH3); 1.25-1.68(32H, m., 16CH2); 2.55-2.59

    (2H, m., =C-CH2-); 2.75-2.79 (2Н, m., -CH2C9H19); 6.96 (1H, d., 3J=5.1 Hz, Th-4’-Н); 7.04 (1H, d., 3J=3.7 Hz,

    Th-3-Н); 7.12 (1H, d., 3J=3.7 Hz, Th-4-Н); 7.23 (1H, d., 3J=5.1 Hz, Th-5’-Н); 9.75 (1 H, s., CНO); Z-(11): 0.86-

    0.90 (6H, m., 2СH3); 1.25-1.68 (32H, m., 16CH2); 2.63-2.66 (2H, m., =C-CH2-); 2.75-2.79 (2Н, m., -

    C(O)CH2CH2C9H19); 6.97 (1H, d., 3J=5.1 Hz, Th-4’-Н); 7.14 (1H, d., 3J=3.8 Hz, Th-3-Н); 7.26 (1H, d., 3J=5.1 Hz,

    Th-5’-Н); 7.57(1H, d., 3J=3.8 Hz, Th-4-Н); 10.36 (1 H, s., CНO).

    13C NMR (100 MHz, δ, ppm): E-(11): 14.14 (СН3); 22.70, 27.84, 28.72, 29.35, 29.38, 29.42, 29.44, 29.46,

    29.49, 29.55; 29.58; 29.62; 29.68; 29.72; 29.76; 29.84; 30.57; 31.91 (18СН2); 125.03 (3-Th); 125.33 (5’-Th);

    129.32 (Cl-С=); 130.36 (4’-Th); 131.98 (=С-CHO); 132.93 (4-Th); 137.31(2’-Th); 141.03 (2-Th); 141.32 (3’-Th);

    142.20 (5-Th); 189.73(СHO). Z-(11): 28.55, 28.30 (2СН2); 125.12 (3-Th); 125.75 (5’-Th); 130.47 (4’-Th);

    135.05 (4-Th); 137.98 (2’-Th); 140.78(2-Th); 141.08 (3’-Th); 145.87 (5-Th); 192.02 (СHO).

    Elemental analysis. Calculated for C31H47ClOS2: C, 69.56%; H 8.85%. found: C, 69.61%; H, 8.91%.

    Ethyl 3,3''-didecyl-[2,2':5',2''-terthiophene]-5-carboxylate (7d)

    To a mixture of sodium ethoxide (90 mg, 1.3 mmol), ethyl mercaptoacetate

    (0.15 ml, 1.3 mmol) in 4 ml ethanol was added the solutio

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