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S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’- bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4- thiadiazole and 1,2,4-triazole Anastasia S. Kostyuchenko 1,2 , Vyacheslav L.Yurpalov 1 , Aleksandra Kurowska 3 , Wojciech Domagala 3 , Adam Pron 4 and Alexander S. Fisyuk* 1,2 Address: 1 Department of Organic Chemistry, Omsk F. M. Dostoevsky State University, 55a Mira Ave, 644077 Omsk, Russia, 2 Laboratory of New Organic Materials, Omsk State Technical University, Mira Ave, 11, Omsk 644050, Russia, 3 Department of Physical Chemistry and Technology of Polymers, Silesian University of Technology, Marcina Strzody 9, 44-100 Gliwice, Poland and 4 Faculty 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

bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

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Page 1: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

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Supporting Information

for

Synthesis of new, highly luminescent bis(2,2’-

bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4-

thiadiazole 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

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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:

2

2

RR

Rn

n

m

m

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

13C 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

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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).

1H 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).

13C 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

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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,

3J=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

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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,

3J=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

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(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,

3J=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).

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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,

3J=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).

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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,

3J=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).

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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).

1H 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,

3J=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).

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13C 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-5-

carboxamide (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. 3-

Decyl-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)

1H 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,

Page 11: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S11

4J=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).

13C 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

Page 12: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S12

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

1H NMR (400 MHz, CDCl3)

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

Inte

nsity

18.72 3.462.292.021.020.97 0.95

Chloroform-d

TMS

M05

M00

M04

M01

M03

M02

7.6

47.3

97.3

87.2

37.2

27.1

1 7.1

07.0

9 2.8

12.7

92.7

7

1.7

21.7

11.6

91.6

71.6

5

1.3

91.3

21.2

61.2

3

0.8

90.8

80.8

6

S

S

S

S

O

NN

CH3

CH3

7.2 7.1

Chemical Shift (ppm)

0

0.05

0.10

Inte

nsity

1.021.00

Chloroform-dM05

7.2

67.2

37.2

37.2

2

7.1

17.1

07.1

07.0

9

7.7 7.6 7.5 7.4

Chemical Shift (ppm)

0

0.1

0.2

Inte

nsity

0.97 0.95

7.6

4

7.3

97.3

97.3

8

13C NMR (100MHz)

180 160 140 120 100 80 60 40 20 0

Chemical Shift (ppm)

-1.0

-0.5

0

0.5

1.0

Inte

nsity

Chloroform-d

TMS

160.0

1 140.5

1140.2

8135.9

4134.7

6

132.3

6

127.7

0127.0

3126.6

4

121.9

9

77.3

677.0

476.7

2

31.9

1

29.6

129.5

829.3

422.7

0

14.1

2

0.0

0

S

S

SS

O

NN

CH3

CH3

Page 13: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S13

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

1H NMR (400 MHz, CDCl3)

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Inte

nsity

3.332.231.081.05 0.98

Chloroform-d

TMS

7.5

57.5

47.4

27.4

2 7.4

17.2

6

7.0

77.0

67.0

5

6.5

3

4.2

84.2

64.2

54.2

3

1.3

51.3

31.3

1

0.0

0

S

Cl

O

OCH3

7.55 7.50 7.45 7.40

Chemical Shift (ppm)

0

0.05

0.10

Inte

nsity

1.05 1.00

7.5

67.5

57.5

57.5

4

7.4

27.4

27.4

17.4

0

7.15 7.10 7.05 7.00 6.95

Chemical Shift (ppm)

0

0.05

0.10

Inte

nsity

1.08

7.0

77.0

77.0

67.0

5

13C NMR (100MHz)

180 160 140 120 100 80 60 40 20 0

Chemical Shift (ppm)

-1.0

-0.5

0

0.5

Inte

nsity

Chloroform-d

TMS

164.0

1

141.0

9

129.4

6

128.0

8

113.3

9

77.3

777.0

576.7

4

60.5

7

14.2

7

0.0

0

S

Cl

O

O

CH3

Page 14: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S14

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

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

Inte

nsity

3.412.261.091.060.78

Chloroform-d

TMS

9.6

9

7.3

2 7.3

17.2

87.2

87.2

6

7.0

5

6.8

2

4.3

94.3

74.3

54.3

4

1.4

01.3

81.3

6

0.0

0

S

S

OH

O

OCH3

7.30 7.25

Chemical Shift (ppm)

0

0.025

0.050

0.075

Inte

nsity

1.061.03

Chloroform-d

7.3

2 7.3

27.3

1 7.3

1

7.2

97.2

97.2

87.2

8

7.2

6

7.05 7.00

Chemical Shift (ppm)

0

0.025

0.050

0.075

Inte

nsity

1.097.0

57.0

47.0

47.0

3

13C NMR (100MHz)

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0

Chemical Shift (ppm)

-1.0

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0.4

Inte

nsity

Chloroform-d

TMS

164.4

7

142.3

2

136.4

8

128.1

4126.6

3125.4

0

114.9

6

77.3

677.0

376.7

2

61.0

7

14.3

7

0.0

0

S

S

OH

O

OCH3

Page 15: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S15

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

1H NMR (400 MHz, CDCl3)

1H FAS704_001001R_FINAL.ESP

10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

-0.02

-0.01

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

0.16

0.17

0.18

0.19

0.20

0.21

Norm

alized Inte

nsity

3.007.012.002.002.002.020.981.041.001.01

CHLOROFORM-d

TMS

7.3

2 7.3

07.2

9

7.2

87.2

77.0

6

6.9

0

4.3

54.3

3 4.3

14.1

74.1

64.1

4

1.8

9

1.8

71.8

51.8

31.8

11.5

31.5

11.3

81.3

71.3

51.3

4

0.9

30.9

20.9

0

S

S

O

O

O

CH3

CH3

1H FAS704_001001R_FINAL.ESP

7.35 7.30 7.25 7.20 7.15

Chemical Shift (ppm)

0

0.025

0.050

Norm

alized Inte

nsity

1.001.01

7.3

27.3

27.3

1 7.3

07.2

9

7.2

87.2

87.2

7

1H FAS704_001001R_FINAL.ESP

7.05 7.00 6.95 6.90 6.85

Chemical Shift (ppm)

0

0.025

0.050

0.075

Norm

alized Inte

nsity

0.981.04

7.0

67.0

57.0

57.0

4

6.9

0

13C NMR (100MHz)

13C FAS704_001000FID_FINAL.ESP

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8

Chemical Shift (ppm)

-0.50

-0.45

-0.40

-0.35

-0.30

-0.25

-0.20

-0.15

-0.10

-0.05

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

Norm

alized Inte

nsity

Chloroform-d

TMS

161.7

0161.0

9

141.0

3

136.6

9

128.1

2126.1

2124.9

7

112.9

4

108.2

5

72.1

1

60.4

2

31.5

0 29.3

0

25.4

7

22.5

5

14.3

914.0

0

S

S

O

CH3

O

O

CH3

Page 16: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S16

4-(Hexyloxy)-2,2'-bithiophene-5-carboxylic acid (9). 1H NMR (400 MHz, (CD3)2CO)

1H FAS846_001000FID.ESP

10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

Norm

alize

d In

tensi

ty

3.374.082.042.052.000.980.980.980.94

Acetone-d6

TMS

7.4

77.4

6

7.3

8 7.3

87.1

9

7.0

67.0

67.0

5 4.2

34.2

14.1

9

2.7

0

1.7

91.7

7 1.7

51.7

31.4

91.4

7 1.4

51.4

11.3

01.2

91.2

91.2

8

0.8

50.8

30.8

1

S

S

O

O

OH

CH3

1H FAS846_001000FID.ESP

7.50 7.45 7.40 7.35

Chemical Shift (ppm)

0

0.1

0.2

Norm

alize

d In

tensi

ty

0.980.94

7.4

8 7.4

77.4

6 7.4

6

7.3

87.3

8 7.3

87.3

7

1H FAS846_001000FID.ESP

7.25 7.20 7.15 7.10 7.05 7.00

Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

Norm

alize

d In

tensi

ty

0.980.98

7.1

9

7.0

77.0

67.0

67.0

5

13C NMR (100MHz)

200 180 160 140 120 100 80 60 40 20 0

Chemical Shift (ppm)

-0.05

0

0.05

Inte

nsity

Acetone-d6 Acetone-d6

TMS

204.1

6

160.2

3159.6

8

139.9

2

135.2

7

127.2

7124.3

4

112.5

9

107.3

7

71.0

0

30.1

828.1

324.1

721.2

4

12.2

6

0.0

0

S

S

O

OH

O

CH3

Page 17: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S17

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

1H NMR (400 MHz, CDCl3)

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5

Chemical Shift (ppm)

-0.02

-0.01

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

0.16

0.17

0.18

0.19

Inte

nsity

3.90 1.631.031.03 1.030.49 0.43

Chloroform-d

TMS

10.1

3

7.3

1 7.2

97.2

87.2

77.0

67.0

56.9

2

4.2

64.2

44.2

3

2.0

01.9

91.9

71.9

51.9

3

1.5

51.5

31.3

81.3

71.2

51.2

20.9

30.9

10.9

0

0.0

0

S

S

O

NH

O

CH3

NH

O

S S

O

CH3

7.4 7.3 7.2 7.1 7.0 6.9

Chemical Shift (ppm)

0

0.05

0.10

0.15In

tensity

1.03 0.55 0.43

Chloroform-d

7.3

17.2

97.2

87.2

77.2

6

7.0

67.0

57.0

3

6.9

2

13C NMR (100MHz)

180 160 140 120 100 80 60 40 20 0

Chemical Shift (ppm)

-0.5

0

0.5

Inte

nsity

Chloroform-d

TMS

156.7

5156.5

0

140.8

8

136.7

1

128.2

1

125.0

1

112.0

1

111.9

1

72.7

0

31.3

9 29.1

9

25.4

122.5

9

14.0

2

S S NH

O

O

CH3

NH

O

S

S

O

CH3

Page 18: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S18

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

1H NMR (400 MHz, CDCl3)

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

-0.02

-0.01

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

0.16

0.17

0.18

Inte

nsity

6.38 3.322.042.031.001.00 0.48

7.3

1

7.3

1 7.3

07.2

7

7.0

6

6.9

6

4.2

34.2

24.2

0

2.1

7

1.9

21.9

11.8

91.8

71.8

51.7

21.5

91.5

7 1.5

51.4

01.3

71.3

61.3

51.2

5

0.9

10.8

90.8

8

0.0

0

S

S

O

CH3

O

NN

S S

O

CH3

7.35 7.30 7.25

Chemical Shift (ppm)

0

0.025

0.050

Inte

nsity

1.000.94

7.3

1 7.3

17.3

0 7.3

0

7.2

8 7.2

77.2

67.2

6

7.10 7.05 7.00 6.95

Chemical Shift (ppm)

0

0.05

0.10

0.15

Inte

nsity

1.001.00

7.0

67.0

67.0

57.0

4

6.9

6

13C NMR (100MHz)

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

Chemical Shift (ppm)

-0.5

0

0.5

1.0

Inte

nsity

Chloroform-d

TMS

158.6

4 158.0

6

139.2

8136.5

7

128.1

7124.7

9

113.2

4

101.3

8

77.3

677.0

476.7

372.3

8

31.6

5 29.4

7

25.5

922.6

3

14.0

6

0.0

0

S

S

O

CH3

O

NN

S S

O

CH3

Page 19: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S19

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

1H NMR (400 MHz, CDCl3)

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Inte

nsity

14.09 3.042.031.991.92 1.751.000.84

Chloroform-d

TMS

M04

M06

M00

M03 M02

M01

7.8

87.6

37.6

27.6

17.4

97.3

57.3

37.3

17.1

87.1

87.0

87.0

7

2.7

42.7

22.7

0

1.6

91.6

3 1.6

2

1.5

81.3

11.2

9 1.2

71.2

5

0.8

90.8

80.8

6

S

S

CH3

NH

O

7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1

Chemical Shift (ppm)

0

0.05

0.10

Inte

nsity

1.92 1.75 1.07 1.000.990.970.84

Chloroform-d

M04M06

7.8

8

7.6

37.6

27.6

1

7.4

9

7.3

67.3

6 7.3

57.3

57.3

37.3

1

7.2

57.1

87.1

87.1

87.1

77.1

47.1

2

7.1

07.0

87.0

87.0

7

13C NMR (100MHz)

200 180 160 140 120 100 80 60 40 20 0

Chemical Shift (ppm)

-1.0

-0.5

0

0.5

Inte

nsity

Chloroform-d

TMS

159.9

2

140.2

5137.7

3136.2

9135.8

0135.0

5

131.5

2129.0

7127.6

2126.9

9120.3

0

77.3

677.0

476.7

3

31.9

1

29.6

129.3

3

22.6

9

14.1

1

0.0

0

S

S

CH3

O

NH

Page 20: bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole,

S20

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

1H NMR (400 MHz, CDCl3)

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Inte

nsity

32.40 6.734.123.54 2.041.94

Chloroform-d

TMS

M04

M06

M07

M05

M08

M00

M03

M09

M02

M01

7.7

07.6

9

7.6

9 7.6

57.6

37.4

77.4

57.2

97.2

87.2

67.0

67.0

57.0

27.0

16.8

3

2.6

12.5

92.5

7

1.4

71.4

5

1.3

11.2

91.2

61.2

3

0.9

00.8

90.8

7

S

S

CH3

N

NNS

S

CH3

7.70 7.65 7.60 7.55 7.50 7.45 7.40

Chemical Shift (ppm)

0

0.05

0.10

Inte

nsity

3.54 2.22

M08M09

7.7

07.6

97.6

97.6

7 7.6

7 7.6

5 7.6

37.6

2 7.6

17.6

1

7.4

87.4

77.4

6 7.4

57.4

5

7.25 7.20 7.15 7.10 7.05 7.00

Chemical Shift (ppm)

0

0.05

0.10

Inte

nsity

2.02 2.001.94

Chloroform-d

M06M07

M05

7.3

07.2

97.2

87.2

87.2

6

7.0

67.0

67.0

57.0

57.0

3

7.0

27.0

1

13C NMR (100MHz)

200 180 160 140 120 100 80 60 40 20 0

Chemical Shift (ppm)

-1.0

-0.5

0

0.5

1.0

Inte

nsi

ty

Chloroform-d

TMS

150

.23

139

.61

135

.09

133

.58

131

.11

130

.58

130

.42

128

.97

127

.46

126

.52

125

.99

125

.77

125

.39

125

.29

77.

3877.

0676.

74 31.

93 29.

6229.

3528.

9622.

70

14.12

0.0

0

S

S

CH3

N

NN

S

S

CH3