Supporting information for

Supporting Information for

Synthesis of new, highly luminescent bis(2,2’bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4thiadiazole and 1,2,4-triazole

Anastasia S. Kostyuchenko1,2, Vyacheslav L.Yurpalov1, Aleksandra Kurowska3, Wojciech Domagala3, Adam Pron4 and Alexander S. Fisyuk*1,2

Address: 1Department of Organic Chemistry, Omsk F. M. Dostoevsky State University, 55a Mira Ave, 644077 Omsk, Russia, 2Laboratory of New Organic Materials, Omsk State Technical University, Mira Ave, 11, Omsk 644050, Russia, 3Department of Physical Chemistry and Technology of Polymers, Silesian University of Technology, Marcina Strzody 9, 44-100 Gliwice, Poland and 4Faculty of Chemistry Warsaw University of Technology, Noakowskiego 3, 00-664 Warszawa, Poland * Corresponding author Email: Alexander S. Fisyuk - [email protected]

Experimental part

Table of Contents General information.................................................................................................S2 Experimental procedures and analytical data..........................................................S3 References……………………………………………………………………………….S11

S1

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. UV–vis spectra were taken in dichloromethane solutions using a Hewlett Packard 8453 diode-array spectrometer, while fluorescence spectra were recorded on Hitachi F-2500 fluorescence spectrometer. The frontier molecular orbital (HOMO–LUMO) gaps of investigated compounds were estimated from the onset of their –* absorption band. Fluorescence excitation spectra were recorded to determine the excitation wavelength at which the maximum fluorescence response is observed. Subsequent fluorescence emission spectra were recorded at excitation wavelengths determined in this manner. The quantum yield of examined compounds was determined relative to 9,10-diphenylanthracene – a known quantum yield standard, using comparative method [1,2]. Using this method, the quantum yield is calculated according to the following equation:

 m   n2     2     R    mR   nR  where: Φ is the quantum yield, m is the slope of origin approaching linear segment of the plot of integrated fluorescence intensity vs absorbance of a fluorophore solution, n is the refractive index of solvent and subscript R refers to data for the solution of reference fluorophore of known quantum yield – here: 9,10-diphenylanthracene in ethanol (ФR = 0.950 for excitation at 330–380 nm) and in cyclohexane (ФR = 0.955 for excitation at 366 nm) [3]. The 1H and 13C NMR spectra were obtained in CDCl3 with TMS as an internal standard, using a Bruker DRX 400 spectrometer (400 and 100 MHz, respectively). The 13

C NMR spectra were obtained in the J-modulation mode. 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 and were visualized

S2

with UV light. All chemicals were of analytical grade and purchased from Sigma-Aldrich Chemical Co.

Experimental and analytical data The synthesis of 1, 2, 3, 8, 10, 11, 15 is described in detail in Supporting Information of reference [4]. 2,5-Bis(3-decyl-2,2'-bithiophene-5-yl)-1,3,4-oxadiazole (13). A mixture of 11 (0.41 g, 0.6 mmol) and phosphorus oxychloride (7.58 g, 49.4 mmol) was refluxed for 5 h (the completion of the reaction was monitored by TLC). The resulting solution was cooled to room temperature, and poured on a mixture of crushed ice (10 g) in water (50 mL). It was then neutralized by saturated solution of NaHCO3. The product was extracted with CHCl3 (3 × 20 mL). The extract was washed with saturated aqueous sodium chloride (30 mL), dried (Na2SO4) and concentrated. Then the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography using benzene as eluent. Yield: 0.40 g (78%); yellow solid; Rf = 0.38 (silica gel, benzene or CH2Cl2) mp 86–87 °С IR (KBr). ν сm-1: 1580 (С=N). 1

H NMR (400 MHz, CDCl3, δ, ppm, J, Hz): 0.88 (t, 3J=6.7 Hz, 6 H, 2СН3), 1.23-1.40

(m, 28H, 14СН2), 1.69 (m, 2Н, ThCH2CH2C8H17), 2.79 (t, 3J=7.8 Hz, 4H, 2Th-CH2), 7.10 (d.d, 3J=4.9 Hz, 3J=3.8 Hz, 2H, 2Th-4'-H), 7.23(d.d, 3J=3.5 Hz, 4J=0.5 Hz, 2H, 2Th-3'-H), 7.38 (d.d, 3J=5.1 Hz, 4J=0.6 Hz, 2H, 2Th-5'-H), 7.64(s, 2H, 2Th-4-H). 13

C NMR (100 MHz, δ, ppm): 14.12 (СH3), 22.70, 29.27, 29.34, 29.43, 29.50, 29.58,

29.61, 30.47, 31.91 (СH2), 121.99 (2-Th), 126.64 (3′-Th), 127.03(5′-Th), 127.70(4′-Th), 132.36 (2-Th), 134.76 (5-Th), 135.94 (3-Th), 140.51 (2′-Th), 160.01 (2,5-Oxadiazole) Elemental analysis. Calculated for С38H50N2S5: %C = 65.66, %H = 7.25, %N = 4.03; found: %C = 65.56, %H = 7.28, %N = 4.13

S3

Ethyl 3-oxo-3-(2-thienyl)propanoate (4). Compound 4 was prepared according to the known procedure [5] (see Supporting Information). Yield 87%. B.p. 164-168 °C (15-18 mmHg), lit. 143 °C (7 mmHg).

Ethyl 3-chloro-3-(2-thienyl)acrylate (5) 5.0 g (25 mmol) of freshly distilled compound 4 was slowly added with stirring to 11.5 mL (125 mmol) of phosphoryl chloride under cooling. Then 3.9 mL (28 mmol) of dry triethylamine was added drop-wise during ca. 30 min. After the addition of 0.1 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) the reaction mixture was stirred for 30 min in an ice bath, then for 6 h at 60–70 °C and finally left overnight at rt. The excess of POCl3 was removed under vacuum and the resulting mixture was treated with 100 g of crushed ice. The product was extracted with dichloromethane (4 × 20 mL) and dried over sodium sulfate. After removal of the solvent on a rotary evaporator, the final residue was purified by column chromatography (SiO2/hexane-ethyl acetate 9:1) yielding 4.1 g (76%) of yellow oil. Rf 0.35 (hexane-ethyl acetate 9:1). IR (ν, cm-1): 1606 (C=C), 1721 (C=O), 2981 (C-Halk), 3106 (C-Har). NMR 1Н (СDCl3, δ, ppm, J, Hz): 1.33 (3H, t, 3J= 7.1, ОСН2CH3); 4.26 (2H, q, 3J= 7.2, ОСН2CH3); 6.53 (1H, s, C(Cl)=CH); 7.06 (1H, dd, 3J=5.0, 3J=3.8, Th-4-Н); 7.41 (1H, dd, 3

J=5.1, 4J=1.0, Th-5-Н); 7.55 (1 H, dd, 3J=3.8, 4J=1.1, Th-3-Н);

NMR 13С (СDCl3, δ, ppm): 14.27 (ОСН2CH3), 60.57(ОСН2CH3), 113.39 (C(Cl)=CH), 128.09 (3(C)- Th), 129.16 (5(C)- Th),129.46 (4(C)- Th), 141.09 (2(C)- Th), 164.01 (С=O). Elemental analysis. Calculated for C9H9ClO2S: %C = 49.89, %H = 4.19; found: %C = 48.56, %H = 4.28

S4

Ethyl 4-hydroxy-2,2'-bithiophene-5-carboxylate (6). 2.2 mL (20 mmol) of ethyl thioglycolate was added to a solution of sodium ethylate, prepared from 0.92 g (40 mmol) of sodium and 75 mL of dry ethanol. The resulting mixture was stirred for an additional 15 min under nitrogen. Then the solution of 4.0 g (18 mmol) of 5 in 5 mL of dry ethanol was added dropwise to the resulting suspension and stirred for 1.5 h under an inert atmosphere. The reaction mixture was concentrated in vacuum, dissolved in 150 mL of water, cooled and acidified with 2 М HCl to pH 3–4. The precipitate was filtered out, then washed with water to pH 7. Recrystallization from methanol gave 2.2 g (49%) of white powder. Mp 70–71 °C (methanol). IR (ν, cm-1): 1097 (C-O-C), 1645 (C=O), 3083 [Wight] (O-H). NMR 1Н (СDCl3, δ, ppm, J, Hz): 1.38 (3H, t, 3J= 7.1, ОСН2CH3); 4.36 (2H, q, 3J= 7.2, ОСН2CH3); 6.28 (1H, s, Th-3-Н); 7.04 (1H, dd, 3J=5.1, 3J=3.7, Th-4’-Н); 7.28 (1H, dd, 3

J=3.7, 4J=1.2, Th-5’-Н); 7.32 (1 H, dd, 3J=5.1, 4J=1.0, Th-3’-Н), 9.69 (1H, s, OH);

NMR 13С (СDCl3, δ, ppm): 14.37 (ОСН2CH3), 61.07(ОСН2CH3), 114.96 (3’(C)- Th), 125.40 (3(C)- Th), 126.63 (5’(C)- Th), 128.14 (4’(C)- Th), 136.48 (4(C)- Th), 142.32 (2’(C)- Th), 164.47 (С=O). Elemental analysis. Calculated for C11H10O3S2: %C = 51.95, %H = 3.96; found: %C = 52.06, %H = 4.03

Ethyl 4-(hexyloxy)-2,2'-bithiophene-5-carboxylate (7). Potassium tert-butylate (0.86 g, 7.7 mmol) was added to a solution of 1.7 g (6.7 mmol) of 6 in 14 mL of dry DMSO under nitrogen and the resulting mixture was stirred for 15 min. After the drop-wise addition of 1.56 g (7.2 mmol) of 1-iodohexane to this mixture, it was stirred under inert atmosphere for 4 h, then poured into 150 mL of ice water. The product was extracted with dichloromethane (4 × 25 mL). The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuum. Purification by the column chromatography

S5

(SiO2/hexane-ethyl acetate 9:1) yielded 1.83 g (81%) of 7 as a green solid. Mp 40– 42 °C (hexane-ethyl acetate 9:1). Rf 0.39 (hexane-ethyl acetate 9:1). IR (ν, cm-1): 1092 (C-O-C), 1700 (C=O); 2851, 2953 (C-Halk); 3098 (C-Har). NMR 1Н (СDCl3, δ, ppm, J, Hz): 0.92 (3H, t, 3J= 7.0, ОСН2CH3); 1.33-1.38 (7H, m, (СН2)2, CH3) 1.50 (2H, m, CH2), 1.83 (2H, dd, 3J=14.9, 3J=6.9, CH2), 4.15 (2H, t, 3J=6.7, OCH2), 4.31 (2H, q, 3J=7.0, ОСН2CH3); 6.90 (1H, s, Th-3-Н); 7.04 (1H, dd, 3J=5.1, 3

J=3.5, Th-4’-Н); 7.27 (1H, dd, 3J=3.7, 4J=1.2, Th-5’-Н); 7.30 (1H, dd, 3J=5.1, 4J=1.2,

Th-3’-Н); NMR 13С (СDCl3, δ, ppm): 14.00 (ОСН2CH3), 14.39 (CH3), 22.55, 25.47, 29.30, 31.50 ((CH2)4), 60.42 (ОСН2CH3), 72.11 (ОСН2CH2), 112.94 (3(C)- Th), 124.97 (3’(C)- Th), 126.45 (5’(C)- Th), 128.12 (4’(C)- Th), 136.69 (2(C)- Th), 141.03 (2’(C)- Th), 161.09 (4(C)- Th), 161.70 (С=O). Elemental analysis. Calculated for C17H22O3S2: %C = 60.32, %H = 6.55; found: %C = 60.38, %H = 6.61

4-(Hexyloxy)-2,2'-bithiophene-5-carboxylic acid (9). 1.0 g (3 mmol) of 7 dissolved in 5 mL of dry ethanol was added to a solution of 0.5 g (9 mmol) of potassium hydroxide in 8 mL of dry ethanol. The reaction mixture was heated to 50–60 °C and stirred for 4 h, then cooled to rt and concentrated in vacuum. The residue was dissolved in 20 mL of water and acidified with 2 M HCl to pH 3–4. The resulting suspension was vigorously stirred for 20 min and filtered out. The precipitate was washed with ice water and dried. Recrystallization from methanol gave 0.79 g (87%) of 9 as a white powder. Mp 134–136 °C (methanol). IR (ν, cm-1): 1097 (C-O-C), 1649 (C=O), 2556 (C(=O)OH); 2857, 2947 (C-Halk); 3088 (C-Har).

S6

NMR 1Н ((СD3)2CO, δ, ppm, J, Hz): 0.83 (3H, t, 3J= 7.0, СН2CH3); 1.25-1.32 (4H, m, (СН2)2) 1.45 (2H, m, CH2), 1.75 (2H, m, CH2), 2.68 (s, OH), 4.21 (2H, t, 3J=6.7, OCH2); 7.06 (1H, dd, 3J=5.1, 3J=3.5, Th-4’-Н); 7.19 (1H, s, Th-3-Н); 7.38 (1H, dd, 3

J=3.7, 4J=1.2, Th-5’-Н); 7.47 (1H, dd, 3J=5.1, 4J=1.2, Th-3’-Н);

NMR 13С ((СD3)2CO, δ, ppm): 12.26 (CH3), 21.24, 24.17, 28.13, 30.18 (4CH2), 71.00 (ОСН2CH2), 107.37 (5(C)- Th), 112.59 (3(C)- Th), 124.34 (3’(C)- Th), 125.71 (5’(C)- Th), 127.27 (4’(C)- Th), 135.27 (2(C)- Th), 139.92 (2’(C)- Th), 159.68 (4(C)- Th), 160.23 (С=O). Elemental analysis. Calculeted for C15H18O3S2: %C = 58.04, %H = 5.84; found: %C = 58.08, %H = 5.91

N,N’-Bis[4-(hexyloxy)-2,2’-bithiophen-5-oyl]hydrazine (12). Oxalyl chloride (0.64 mL, 7.6 mmol) was added to a suspension of 9 (0.59 g, 1.9 mmol) in 6 mL of dry dichloromethane under cooling (ice bath). After the addition of one drop of DMF to the resulting mixture, it was stirred for 30 min under cooling then at rt for additional 2.5 h. The solvent and the excess of oxalyl chloride were removed under reduced pressure and the final product (acid chloride) was used in subsequent reactions without further purification. Crude acid chloride was dissolved in 12 mL of dichloromethane, cooled in an ice bath. Then, a mixture of 0.048 mL (0.95 mmol) of hydrazine hydrate and 0.92 mL (11 mmol) of dry pyridine in 3 mL of dichloromethane was added dropwise. The reaction mixture was stirred for 30 min under cooling and left overnight at rt. After removal of the solvent in vacuum the residue was treated with 10 mL of ice water and stirred for 15 min. The precipitate was filtered out, washed with water and dried. Recrystallization from methanol gave 0.35 g (60%) of 12 as a dark yellow solid. Mp 168–170 °C (methanol). Rf 0.67 (chloroform). IR (ν, cm-1): 1110 (C-O-C), 1608 (C=O); 2852, 2948 (C-Halk); 3080 (C-Har), 3348 (N-H).

S7

NMR 1Н (СDCl3, δ, ppm, J, Hz): 0.91 (3H, m, СН2CH3); 1.38 (4H, m, (СН2)2) 1.53 (2H, m, CH2), 1.97 (2H, m, CH2), 4.24 (2H, t, 3J=6.7, OCH2); 6.92 (1H, s, Th-3-Н); 7.05 (1H, m, Th-4’-Н); 7.27 (1H, m, Thi-5’-Н); 7.29 (1H, m, Th-3’-Н), 10.13 (1H, s, NH); NMR 13С (СDCl3, δ, m.d.): 14.02 (СН2CH3), 22.59, 25.41, 29.19, 31.39 ((CH2)4), 72.70 (ОСН2CH2), 111.91 (5(C)- Th), 112.01 (3(C)- Th), 125.01 (3’(C)- Th), 126.12 (4’(C)- Th), 128.21 (5’(C)- Th), 136.71 (2(C)- Th), 140.88 (2’(C)- Th), 156.50 (4(C)- Th), 156.75 (С=O). Elemental analysis. Calculeted for C30H36N2O4S4: %C = 58.41, %H = 5.88, %N = 4.54; found: %C = 58.43, %H = 5.90, N = 4.60

2,5-Bis[4-(hexyloxy)-2,2’-bithiophen-5-yl]-1,3,4-oxadiazole (14). A mixture of 0.20 g (0.32 mmol) of 12 and 3 mL of phosphoryl chloride was heated to 60–70 °C and stirred for 6 h, then cooled to rt, poured in small portions into 100 g of crushed ice. The product was extracted with chloroform (4 × 20 mL). The combined organic layers were washed with 30 mL of ice water and the solvent was removed in vacuum. Chromatography purification (SiO2/benzene-ethyl acetate 20:1) of the final residue gave 0.14 g (83%) of 14 as a bright yellow powder. Mp 104–106 °C (chloroform). Rf 0,53 (chloroform). IR (ν, cm-1): 1113 (C-O-C); 1572, 1593 (C=N); 2852, 2926 (C-Halk); 3079, 3109 (C-Har). NMR 1Н (СDCl3, δ, ppm, J, Hz): 0.89 (6H, m, СН2CH3); 1.33 (8H, m, (СН2)2) 1.55 (4H, m, CH2), 1.89 (4H, m, CH2), 4.22 (4H, t, 3J=6.5, OCH2); 6.96 (2H, s, Th-4-Н); 7.05 (2H, dd, 3J=5.1, 4J=3.5, Th-4’-Н); 7.27 (2H, dd, 3J=3.6, 4J=1.1, Thi-5’-Н); 7.30 (2H, dd, 3

J=5.2, 4J=1.1, Th-3’-Н);

NMR 13С (СDCl3, δ, m.d.): 14.06 (СН2CH3), 22.63, 25.59, 29.47, 31.65 ((CH2)4), 72.38 (ОСН2CH2), 101.38 (2(C)- Th), 113.24 (4(C)- Th), 124.79 (3’(C)- Th), 125.96 (5’(C)- Th), 128.17 (4’(C)- Th), 136.57 (5(C)- Th), 139.28 (2’(C)- Th), 158.06 (С=N), 158.64(4(C)Th).

S8

Elemental analysis: Calculeted for C30H34N2O3S4: %C = 60.17, %H = 5.72, %N = 4.68; found: %C = 60.20, %H = 5.78, N = 4.70

3-Decyl-N-phenyl-2,2'-bithiophene-5-carboxamide (16). Oxalyl chloride (2.9 mL, 34 mmol) was added drop-wise into an anhydrous CH2Cl2 solution of 3-decyl-2,2'bithiophene-5-carboxylic acid (8, 1.99 g, 5.7 mmol) under vigorous stirring at 0 °С. The reaction mixture was then additionally stirred at room temperature overnight. The solvent and the excess of oxalyl chloride were evaporated under reduced pressure. The resulting 3-decyl-2,2'-bithiophene-5-carboxylic acid chloride was used without purification in the subsequent reaction. Aniline (5.7 mmol) was dissolved in dry ethyl acetate (10 mL) in the presence of triethylamine (1.1 mL, 7.9 mmol). A solution of the acid chloride (5.7 mmol) in 10 mL dry ethyl acetate was added drop-wise. A precipitate was formed, and the mixture was stirred at room temperature overnight. Then, the solvent was removed under reduced pressure. Water (7 mL) was added, and the solid was collected on a filter, then washed three times with water. The resulting crude product was purified by crystallization from methanol. Yield: 2.06 g (82%); white solid; Rf = 0.59 (silica gel, hexane/EtOAc, 5/1) mp 88–90 °С (methanol) IR (ν, cm-1): 1631 (С=О), 3340 (N-H). 1

H NMR (400 MHz, CDCl3, δ, ppm, J, Hz): 0.88 (t, 3J=6.8 Hz, 3 H, СН3), 1.25-1.35 (m,

14H, 7СН2), 1.62 (m, 2Н, ThCH2CH2C8H17), 2.72 (t, 3J=7.8 Hz, 4H, Th-CH2), 7.06-7.08 (d.d, 3J=5.1 Hz, 3J=3.6 Hz, 2H, 2Th-4'-H), 7.10-7.14 (m, 1H, Ph-4-H), 7.17 (d.d, 3J=3.6 Hz, 4J=1.2 Hz, 2H, 2Th-3'-H), 7.31-7.35 (m, 2H, Ph-3,5-H), 7.35 (d.d, 3J=5.2 Hz, 3

J=3.6 Hz, H, Th-4'-H), 7.36(d.d, 3J=5.1 Hz, 4J=1.2 Hz, 2H, 2Th-5'-H), 7.49 (s, 1H, Th-4-

H), 7.61-7.63 (m, 2H, Ph-3,5), 7.88 (s, 1H, -NH-Ph).

S9

13

C NMR (100 MHz, δ, ppm): 14.11 (СH3), 22.69, 29.33, 29.42, 29.48, 29.58, 29.61,

30.53, 31.91 (СH2), 120.30 (2,6-Ph), 124.55 (4-Ph), 126.51(3′-Th), 126.99 (4′-Th), 127.62 (5′-Th), 129.07 (3,5-Ph), 131.52 (4-Th), 135.05 (2-Th), 135.80 (3-Th), 136.29 (5-Th), 137,73 (2′-Th), 140.25 (1-Ph) 159.92 (-C(O)-NHPh). Elemental analysis: Calculeted for C25H31NOS2: %C =70.54, %H =7.34, %N =3.29; found: %C = 70.46, %H = 7.40, %N = 3.33

3,5-Bis(3-decyl-2,2'-bithiophen-5-yl)-4-phenyl-4H-1,2,4-triazole (18). PCl5 (0.23 g, 1.13 mmol) was added to a solution of 3-decyl-N-phenyl-2,2'-bithiophene-5carboxamide (16, 0.50 g, 1.13 mmol) in 3 mL of anhydrous benzene placed in an ice bath. Then, the reaction mixture was stirred for 12 h at rt. After removing the solvent under reduced pressure, the crude product was washed with dry methanol by decantation. Residual amounts of methanol were removed on a vacuum evaporator. 3Decyl-N-phenyl-2,2'-bithiophene-5-carboximidoyl chloride (17) was used at once in the subsequent reaction. A mixture of 17 (1.13 mmol) and hydrazide 10 (0.41 g, 1.13 mmol) in anhydrous N,N‐dimethylacetamide (5 mL) was heated at 165 °C for 6 h under nitrogen (the completion of the reaction was monitored by TLC). The solvent was removed under reduced pressure. 17 was purified by recrystallization from hexane or by column chromatography using benzene/EtOAc (20/1) or CH2Cl2 as eluent. Yield: 0.52g (62%); white solid; Rf = 0.29 (silica gel, /EtOAc, 20/1) mp 96–98 °С IR (ν, cm-1) : 1497 (N=N) 1

H NMR (400 MHz, CDCl3, δ, ppm, J, Hz): 0.89 (t, 3J=6.8 Hz, 6 H, 2СН3), 1.23-1.32

(m, 28H, 14СН2), 1.45 (m, 2Н, ThCH2CH2C8H17), 2.59(t, 3J=7.7 Hz, 4H, 2Th-CH2), 6.83 (s,2Th-4-H), 7.02 (d.d, 3J=5.1 Hz, 3J=3.5 Hz, 2H, 2Th-4'-H), 7.06 (d.d, 3J=3.5 Hz,

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4

J=1.2 Hz, 2H, 2Th-3'-H), 7.29 (d.d, 3J=5.1 Hz, 4J=1.2 Hz, 2H, 2Th-5'-H), 7.45-7.48 (m,

2H, Ph-2,6-H), 7.61-7.71 (m, 3H, Ph-3,5,4-H). 13

C NMR (100 MHz, δ, ppm): 14.12 (СH3), 22.70, 28.96, 29.27, 29.35, 29.40, 29.54,

29.62, 30.18, 31.93 (СH2), 125.39 (2-Th), 125.99 (2,6-Ph), 126.52 (4-Ph), 127.46 (3′-Th), 128.97 (5′-Th), 130.42 (4′-Th), 130.58 (3,5-Ph), 131.11 (4-Th), 133.58 (5-Th), 134.45 (3-Th), 135.09 (2′-Th), 139.61 (1,3,4-Triazole), 150.23 (1-Ph). Elemental analysis: Calculated for C44H55N3S4: %C =70.07, %H =7.35, %N =5.57; found: %C = 70.06, %H = 7.38, %N = 5.60

References 1. Williams, A. T. R.; Winfield, S. A.; Miller, J. N. Analyst, 1983, 108, 1067-1071. 2. Allen, M. W.; Measurement of Fluorescence Quantum Yields, Thermo Fisher Scientific technical note 52019, Madison, WI, USA. 3. Brouwer, A. M. Pure and Applied Chemistry, 2011, 83, 2213-2228. 4. K. Kotwica, E. Kurach, G. Louarn, A. S. Kostyuchenko, A. S. Fisyuk, M. Zagorska, A. Pron. Electrochimica Acta, 2013, 111, 491– 498 5. Y. Jiang; X. Chen; Y. Zheng; Z. Xue; C. Shu; W. Yuan; X. Zhang, Angew. Chem. Int. Ed., 2011, 50, 7304–7307

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2,5-bis(3-decyl-2,2'-bithiophene-5-yl)-1,3,4-oxadiazole (BThOxDiaz) (13) 1

H NMR (400 MHz, CDCl3) M02

TMS

M01

1.26

H3C

CH3

0.45

S

S S

0.40

O S N

Chloroform-d

7.23 7.23 7.22

M05

7.11 7.10 7.10 7.09

0.10

N

0.05 M00

0 1.00

1.02

0.88

Intensity

0.30

7.26

Intensity

0.35

0.25 7.2 7.1 Chemical Shift (ppm) 0.20

7.6 7.5 Chemical Shift (ppm)

7.4

0.89 0.86

2.79

M03

1.71 1.69 1.65 1.67 1.39

7.7

0.05

0.95

1.72

0.97

2.81

0

1.32 1.23

M04

M05

2.77

0.1

7.39 7.38 7.23 7.11 7.22 7.09 7.10

0.10

7.39 7.39 7.38

Intensity

0.15

7.64

7.64

Chloroform-d 0.2

0 0.97 0.95 1.02 11.0

10.5

10.0

9.5

9.0

8.5

8.0

7.5

2.02

7.0

6.5

6.0 5.5 5.0 Chemical Shift (ppm)

4.5

4.0

3.5

3.0

2.29 18.72 2.5

2.0

1.5

3.46 1.0

0.5

13

C NMR (100MHz)

O

S

S

S

CH 3

Chloroform-d

77.36 77.04 76.72

N

121.99

135.94 134.76

140.28

0.5

140.51

160.01

N

29.61 29.58 29.34 22.70

S

1.0

Intensity

31.91

H 3C

0 TMS

0.00

-0.5

14.12

126.64

132.36

127.03 127.70

-1.0

180

160

140

120

100 80 Chemical Shift (ppm)

S12

60

40

20

0

0

Ethyl 3-chloro-3-(2-thienyl)acrylate (5) 1

H NMR (400 MHz, CDCl3)

1.33

0.00

TMS

0.50

Intensity

0.40

Cl

7.07 7.07 7.06 7.05

0.10

0.45

S

0.05

0.35

O

6.53

0 1.08

0.30 6.95

1.35 1.31


4.26 4.25

7.15

0.25 7.42 7.42 7.41 7.40

7.56 7.55 7.55 7.54

Intensity

CH3

O

0.10

0.05 Chloroform-d

1.05

7.55 7.54 7.42 7.42 7.41

0 1.00


7.40 7.26

7.55

4.28 4.23

0.15

7.07 7.06 7.05

Intensity

0.20

0.05

0

11.0

10.5

10.0

9.5

9.0

8.5

8.0

1.05

1.08

0.98

7.5

7.0

6.5

2.23 6.0 5.5 5.0 Chemical Shift (ppm)

4.5

3.33 4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0

13

Cl S

O

77.37 77.05 76.74

Chloroform-d

O

Intensity

164.01

141.09

CH3

0.5

60.57

C NMR (100MHz)

0 TMS

0.00

-0.5

113.39

129.46 128.08

14.27

-1.0

180

160

140

120


S13

60

40

20

0

Ethyl 4-hydroxy-2,2'-bithiophene-5-carboxylate (6) 1 H NMR (400 MHz, CDCl3)

0.20

0.075 0.050 0.025 0

0.00

OH

6.82

Intensity

7.05 7.04 7.04 7.03

1.38

TMS

S

O S

1.09

CH3

1.40 1.36

O

4.37 4.35


0.15

7.26

7.29 7.29 7.28 7.28

7.32 7.32 7.31 7.31

0.075 0.050 0.025 0

Chloroform-d 1.03

1.06

7.32 7.31 7.28 7.28 7.05

0.10

Intensity

Intensity

Chloroform-d

4.39 4.34


9.69

7.26

0.05

0

0.78 11.0

10.5

10.0

1.06 1.09

9.5

9.0

8.5

8.0

7.5

2.26

7.0

6.5


3.41

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0

13

C NMR (100MHz) 77.36 77.03 76.72

S

61.07

Chloroform-d

OH

O S

0.4

142.32 164.47

0.2

CH3

136.48

O 0.3

0.1 0

Intensity

-0.1 -0.2 -0.3 125.40 126.63

-0.4

TMS 0.00

-0.5

14.37

-0.6 114.96

-0.7 -0.8 -0.9 -1.0 128.14

168

160

152

144

136

128

120

112

104

96 88 80 Chemical Shift (ppm)

S14

72

64

56

48

40

32

24

16

8

0

Ethyl 4-(hexyloxy)-2,2'-bithiophene-5-carboxylate (7). 1

H NMR (400 MHz, CDCl3) 1H FAS704_001001R_FINAL.ESP

6.90

TMS

1H FAS704_001001R_FINAL.ESP

CH3

0.19 0.18 0.17

0.075 0.050

0

S

0.16

1.04

0.15

0.98

7.05


0.14 0.13

O S

6.90

O

6.85

CH3

1H FAS704_001001R_FINAL.ESP

0

0.07 1.01 1.00

0.92

1.35 1.38

0.08

CHLOROFORM-d

4.33 4.31 4.16

0.09

0.025

6.90

0.10

7.28 7.28 7.27

0.11

7.32 7.32 7.31 7.30 7.29

0.050

0.12

Normalized Intensity


O

0.025

1.37

0.20

7.06 7.05 7.05 7.04


0.21

0.06

1.89

0.02

1.34

4.17 4.14 4.35

0.03

0.93 0.90

7.15

1.87 1.85

7.20

7.32 7.30 7.29 7.28 7.27 7.06


0.04

1.81 1.83 1.53 1.51

7.35

0.05

0.01 0 -0.01 -0.02 1.01 1.00 1.04 0.98 10.5

10.0

9.5

9.0

8.5

8.0

7.5

7.0

2.02 2.00 6.5

6.0


4.5

2.00 2.00 7.01

4.0

3.5

3.0

2.5

2.0

1.5

3.00 1.0

0.5

0

13

C NMR (100MHz) CH3

Chloroform-d

0.45

S

0.40

O

0.35

CH3

S O 141.03

108.25


0.15

161.70 161.09

0.20

136.69

0.30 0.25

25.47

O

0.50

31.50 29.30

72.11

0.55

22.55

60.42

13C FAS704_001000FID_FINAL.ESP

0.10 0.05 0 -0.05 -0.10 -0.15 -0.20 -0.25 -0.30

128.12

14.39

-0.40 -0.45

14.00

112.94

126.12

-0.35

-0.50

TMS

124.97

160

152

144

136

128

120

112

104

96

88 80 72 Chemical Shift (ppm)

S15

64

56

48

40

32

24

16

8

0

-8

4-(Hexyloxy)-2,2'-bithiophene-5-carboxylic acid (9). 1

H NMR (400 MHz, (CD3)2CO) 1H FAS846_001000FID.ESP

0.70 0.65

7.19

H3C

0.3

7.07 7.06 7.06 7.05


0.75

TMS

1H FAS846_001000FID.ESP

0.4

0.80

Acetone-d6

0.2

O

0.1 0 0.98 7.25

7.20


O

S

0.98

0.60 7.05

7.00

S

0.55

OH 1H FAS846_001000FID.ESP

7.38 7.38 7.38 7.37

0.1

4.21

0

7.50

0.25

0.98


7.35

1.29 1.28 1.77 1.75 1.47 1.73 1.49 1.45 1.41 1.30

4.23 4.19

7.06 7.06 7.05

7.47 7.46

0.15

7.38 7.38

0.20

1.79

2.70

0.10 0.05

0.85 0.83 0.81

0.94

0.30

1.29

0.35

7.19

0.40

0.2

7.48 7.47 7.46 7.46

0.45



0.50

0 0.94 0.98 0.98 0.98 10.5

10.0

9.5

9.0

8.5

8.0

7.5

7.0

2.00 6.5

6.0


4.5

2.05 2.04 4.08 4.0

3.5

3.0

2.5

2.0

1.5

3.37 1.0

0.5

0

13

C NMR (100MHz)

Acetone-d6

Acetone-d6

204.16

CH3

O S

O S

24.17 21.24

28.13

107.37

139.92 135.27

Intensity

160.23 159.68

0.05

30.18

71.00

OH

0

TMS

0.00 12.26

200

180

160

140

112.59

124.34 127.27

-0.05


S16

80

60

40

20

0

N,N’-Bis[4-(hexyloxy)-2,2’-bithiophen-5-oyl]hydrazine (12) 1

H NMR (400 MHz, CDCl3)

Chloroform-d

0.17

7.06 7.05 7.03

7.31 7.29 7.28 7.27 7.26

Intensity

0.18

0.10

0.05 O

0.16 0

S

1.03

0.55

O

O O

0.43

0.91

0.15

S

0.14 7.4

7.3

0.13


7.0

NH

6.9

NH

S

S

4.24

6.92

0.11

1.38 1.37

Chloroform-d

0.12

0.10 0.09

0.93

10.13

Intensity

CH3

6.92

0.15 0.19

0.00

TMS CH3

2.00

0.03 0.02

0.90 1.55

1.93

0.04

1.25 1.22

0.05

1.53

1.97 1.99 1.95

7.06

0.06

4.26 4.23

0.07

7.05

7.31 7.29 7.28 7.27

0.08

0.01 0 -0.01 -0.02 0.49 11.0

10.5

1.03 0.43

10.0

9.5

9.0

8.5

8.0

7.5

7.0

1.03 6.5


4.5

1.03 4.0

3.5

3.0

2.5

2.0

3.90 1.5

1.63 1.0

0.5

0

-0.5

13

C NMR (100MHz)

Chloroform-d CH3

H3C O

NH

NH

S

0.5

112.01

140.88 136.71

Intensity

156.75 156.50

S

31.39 29.19 25.41 22.59

S

O

72.70

S

O O

0

111.91 14.02

125.01

128.21

-0.5

TMS 180

160

140

120


S17

60

40

20

0

2,5-Bis[4-(hexyloxy)-2,2’-bithien-5-yl]-1,3,4-oxadiazole (14) 1

CH3

0.00

H NMR (400 MHz, CDCl3) CH3

0.18 0.17

O S N

0

0.11

0.89

O

S

0.025

0.94

N

1.00

S

2.17

0.12

O

4.22

Intensity

0.050 0.13

7.27 7.26

0.14

7.26

7.31 7.31 7.30 7.30 7.28

0.15

6.96

0.16

S


1.00 7.10

1.00


6.95

0.91

1.92

0.03

1.91 1.89 1.85 1.72 1.87 1.59 1.57 1.55 1.40 1.35 1.25

0 0.04

1.36

7.31 7.30 7.27 7.06

0.05

4.23 4.20

0.05

0.10

7.31

Intensity

0.15

0.06

0.88

0.07

1.37

6.96

0.08

7.06 7.06 7.05 7.04

Intensity

7.35 0.09

0.02 0.01 0 -0.01 -0.02 1.00 10.0

9.5

9.0

8.5

8.0

7.5

1.00

2.03

7.0

6.5

6.0


0.48 2.04 4.0

3.5

3.0

2.5

2.0

6.38

3.32

1.5

1.0

0.5

0

13

C NMR (100MHz) 77.36 77.04 76.73

Chloroform-d CH3

CH3

158.64 158.06

O O S N

N

S

S

Intensity

101.38

139.28 136.57

0.5

72.38

O S

31.65 29.47 25.59 22.63

1.0

0

TMS

170

160

150

140

130

120

110

0.00

124.79 128.17

14.06

113.24

-0.5

100 90 80 70 Chemical Shift (ppm)

S18

60

50

40

30

20

10

0

3-Decyl-N-phenyl-2,2'-bithiophene-5-carboxamide (16) 1

H NMR (400 MHz, CDCl3) TMS

7.49

0.40

1.25

7.35

7.18 7.18 7.18 7.14 7.17 7.12 7.08 7.10 7.08 7.07

7.33

Chloroform-d

7.25

7.31

7.36 7.36 7.35

7.62 7.61 7.63

0.05

H3C

M06

7.88

Intensity

0.10

0.30

M01

M04

0.35

S

O S

0.25

NH

0 1.92

0.97

1.75

M00

0.99 1.07 1.00

7.9

7.8

7.7

7.6

7.5 7.4 Chemical Shift (ppm) M04

7.3

7.2

0.88

Intensity

0.84 0.20

7.1

Chloroform-d M06

1.69 1.63 1.62 1.31 1.58 1.29

1.27

M02

7.88

0.05

M03

2.74 2.72 2.70

7.63

7.31 7.33 7.18 7.18 7.08 7.07

7.62 7.61

0.10

0.89 0.86

7.35

7.49

0.15

0 0.84 1.92 1.751.00 11.0

10.5

10.0

9.5

9.0

8.5

8.0

7.5

1.99

7.0

6.5


4.5

4.0

3.5

3.0

2.03 14.09 2.5

2.0

1.5

3.04 1.0

0.5

0

13

C NMR (100MHz)

O

Intensity

140.25 137.73 136.29 135.80 135.05

159.92

S

0.5

NH

22.69

S

31.91

77.36 77.04 76.73

Chloroform-d

29.61

29.33

H 3C

0 TMS

129.07

200

180

160

140

120.30

-1.0

0.00

14.11

126.99 127.62 131.52

-0.5

120


S19

60

40

20

0

-0.5

3,5-Bis(3-decyl-2,2'-bithiophen-5-yl)-4-phenyl-4H-1,2,4-triazole (BThPhTriaz) (18) 1

H NMR (400 MHz, CDCl3) M09

0.05

1.23

7.47 7.46 7.45 7.45

0

M00

7.70

2.22

7.65


M05 M02

1.26 6.83

7.05 7.05 7.03 7.02 7.01

7.06 7.06

7.30 7.29 7.28 7.28

Chloroform-d S

N

0.05

S

S

S N

7.26

0.20

7.40

M06 M05

Chloroform-d

Intensity

Intensity

7.45

M04

M07

0.10

CH3

H3C

0.89

3.54

0.30

0.25

TMS

7.48

0.35

M01

M08

7.70 7.69 7.69 7.67 7.67 7.65 7.63 7.62 7.61 7.61

Intensity

0.10

N

0 1.94

2.02 2.00

0.15

1.47 1.45 1.31 1.29

7.06

7.65

7.26

7.70 7.69

0.05

7.45

7.69

7.63 7.47

0.10

M03

2.61 2.59 2.57

M09

7.02

M07

0.90 0.87

7.05

M06

7.00 M08

7.05

7.01


7.29 7.28

7.25

0 3.54 11.0

10.5

10.0

9.5

9.0

8.5

8.0

1.94

7.5

2.04 7.0

4.12 6.5


4.5

4.0

3.5

3.0

32.40 6.73

2.5

2.0

1.5

1.0

0.5

0

13

C NMR (100MHz) 31.93 29.62 29.35 28.96 22.70

C H3

H3C

150.23

N

125.39

S S

N

133.58

N S

135.09

S

139.61

1.0

77.38 77.06 76.74

Chloroform-d

125.29

Intensity

0.5

0

125.77

TMS

125.99 126.52 127.46

14.12

128.97 130.42 130.58

-1.0

0.00

131.11

-0.5

200

180

160

140

120


S20

60

40

20

0