Synthesis and photoluminescence properties of star-shaped 2,3,6,7-tetrasubstituted benzo[1,2-b:4,5-b′]difurans

Article abstract of DOI:10.1016/j.dyepig.2016.01.025

A new reaction of α-haloketones with hydroquinones leading to highly fluorescent star-shaped 2,3,6,7-tetrasubstituted benzodifurans is described. Thus 2,3,6,7-tetrakis(4-bromophenyl)-4,8-didecylbenzo[1,2-b:4,5-b′]difuran, the core of benzodifuran stars, w

Full text of DOI:10.1016/j.dyepig.2016.01.025

Accepted Manuscript
Synthesis and Photoluminescence Properties of Star-Shaped 2,3,6,7-Tetrasubstituted
Benzo[1,2-b:4,5-b']difurans
Mariusz J. Bosiak, Piotr Trzaska, Dariusz Kędziera, Jörg Adams
PII:
S0143-7208(16)00036-X
10.1016/j.dyepig.2016.01.025
DYPI 5078
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 4 November 2015
Revised Date: 5 January 2016
Accepted Date: 14 January 2016
Please cite this article as: Bosiak MJ, Trzaska P, Kędziera D, Adams J, Synthesis and
Photoluminescence Properties of Star-Shaped 2,3,6,7-Tetrasubstituted Benzo[1,2-b:4,5-b']difurans,
Dyes and Pigments (2016), doi: 10.1016/j.dyepig.2016.01.025.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Synthesis and Photoluminescence Properties of Star-
Shaped 2,3,6,7-Tetrasubstituted Benzo[1,2-b:4,5-
b']difurans
†
†
†
‡
Mariusz J. Bosiak* , Piotr Trzaska , Dariusz Kędziera , Jörg Adams
†
Department of Organic Chemistry, Faculty of Chemistry, Nicolaus Copernicus University in
Toruń, 7 Gagarin Street, 87-100 Toruń, Poland
‡
Institute of Physical Chemistry, Clausthal University of Technology, Arnold-Sommerfeld-Str. 4,
38678 Clausthal-Zellerfeld, Germany
bosiu@chem.umk.pl
Keywords:
Benzodifurans
Star-Shaped Organic Luminophores
Fluorescence
The Suzuki reaction
MIDA esters
*
Corresponding author: Tel.: +48 512038649; fax: +48 56 6542477; e-mail: bosiu@chem.umk.pl
1

ACCEPTED MANUSCRIPT
ABSTRACT
A new reaction of α-haloketones with hydroquinones leading to highly fluorescent star-
shaped 2,3,6,7-tetrasubstituted benzodifurans is described. Thus 2,3,6,7-tetrakis(4-bromophenyl)-
4,8-didecylbenzo[1,2-b:4,5-b']difuran, the core of benzodifuran stars, was obtained from 1,2-bis(4-
bromophenyl)-2-chloroethanone and 2,5-didecyhydroquinone in the presence of zinc chloride
without a solvent. Elongated benzodifuran derivatives were obtained by the reaction of
tetrabromobenzodifuran with aryl-, heteroaryl- or vinylboronic acid MIDA esters in the presence of
Pd(dppf)Cl catalyst, and tripotassium phosphate as a base in 1,4-dioxane/water mixture. The star-
2
shaped products, obtained in 37-99% yield, exhibit the UV-Vis fluorescence with high quantum
yields, 69-100%. Due to the long-chained alkyl groups at positions 4 and 8, these highly π-
conjugated products are soluble in many organic solvents.
1.
Introduction
The development of efficient photoluminescent materials has been intensively studied during
the last decade. These materials play an important role in optoelectronic devices, such as flat panel
displays [1-4], tunable lasers [5], molecular switches [6], and in photonics [7,8], medicine [9,10],
chemosensors [11-13], solid state lighting [14-17], and organic electroluminescent diodes (OLED)
[18-21]. Benzodifuran (BDF) derivatives, due to their excellent fluorescent properties, represent an
important and little explored group of heterocyclic compounds that can be used for such
applications. Recently, the first examples of benzodifuran small molecule materials [22-33], and
polymers [34-38] have been reported. We also described conjugated benzodifuran systems of
excellent fluorescent quantum yields [39-41] for luminescence application and heteroleptic
ruthenium dyes containing benzodifuran moieties for DSSC applications, which revealed higher
energy conversion efficiency (η) compared to comertially available N719 and Z907 dyes (up to
21% and 46%, respectively) [42]. Herein, the convenient method for synthesis of highly fluorescent
2

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star-shaped π-electronic system containing benzodifuran core and aromatic or heteroaromatic "side
arms" is described.
2.
Experimental
2
.1. Materials and general methods
Experiments with air and moisture sensitive materials were carried under argon atmosphere.
Glassware was oven dried for several hours, assembled hot, and cooled in a stream of argon. Silica
gel 60, Merck 230–400 mesh, was used for preparative column flash chromatography. Analytical
TLC was performed using Merck TLC Silica gel 60 F254 0.2 mm plates. Reagents were
commercially available from Sigma-Aldrich, Merck or Fluorochem and were used without further
purification. [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Pd(dppf)Cl ), potassium
2
phosphate tribasic, and boronic acid MIDA esters were purchased from Sigma–Aldrich. Solvents
were purchased from Avantor and Sigma-Aldrich. 1,4-Dioxane and THF were distilled from
sodium benzophenone ketyl prior to use, N,N-dimethylformamide was stirred over CaH overnight,
2
filtered, and distilled at 20 mmHg prior to use. Dichloromethane, chloroform, acetone, methanol, p-
1
13
xylene, were used without further purification. H and C NMR spectra were recorded on a Bruker
Advance III 400 MHz or Bruker Advance III 700 MHz instrument at ambient temperature.
Chemical shifts are reported in parts per million (δ scale), coupling constants (J values) are listed in
Hertz. IR spectra were recorded on Perkin Elmer FT-IR Spectrometer Spectrum Two. Melting
points were determined with a Büchi SMP 32 and Barnstead-Thermolyne Mel-Temp II apparatus in
open capillaries and are uncorrected. Elemental analyses were performed at Elementary
Analysensysteme GmbH VarioMACRO CHNanalyzer.
2.1.1.Spectroscopic measurements
Dichloromethane (spectrometric grade from Aldrich) was employed as solvent for
absorption and fluorescence measurements. UV/Vis absorption spectra were recorded on a Perkin
3

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Elmer UV-Vis Lambda 25 Spectrometer in a 1-cm quartz cell, in comparison to solvent blank.
Emission spectra were obtained on a Hitachi F-7000 Fluorescence Spectrophotometer and on a
JASCO FP-8500 spectrometer. The quantum yield was determined using 9,10-diphenylanthracene
(
DPA) in cyclohexane (θ = 0.95) at λ = 366 nm. The concentration of DPA and the analyzed
ref ex
substances were set in a way that the absorbance at 366 nm was low enough to avoid the inner filter
effect. The fluorescence life-time was determined using a time-correlated single-photon counting
setup with a Maestro spectrum analyzer (EG&G Ortec, Oak Ridge, USA) and a pulsed LED (376
nm, PicoQuant GmbH, Berlin, Germany) with a pulse width of less than 1.5 ns (FWHM). All
fluorescence light above 406 nm was detected using a low-pass filter. The decay traces were
analyzed assuming a single exponential decay function.
2
.2. Synthesis of the compounds
2.2.1. 2,5-Didecylbenzene-1,4-diol (3)
a)
To
a
stirred mixture of 1,4-dimethoxybenzene (13.81 g, 0.1 mol) and
tetramethylethylenediamine (45 mL, 0.3 mol) in hexane (150 mL), n-butyllithium (2.5 M in hexane,
20 mL, 0.3 mol) was added dropwise at 0 ºC. The mixture was stirred at room temperature for 22
1
h. After coolling to 0 ºC, 1-bromodecane (93.5 mL, 0.45 mol) was added dropwise and the mixture
was stirred at room temperature for 23 h. Water (250 mL) was added and organic layer was
separated. The aqueous layer was washed with diethyl ether (3×75 mL). Combined organic layers
were washed with water (3×50 mL), brine (50 mL) and dried over anhydrous magnesium sulfate.
Solvents were removed on a rotary evaporator and the orange liquid residue was distilled under
vacuum to obtain 32.00 g of pale yellow liquid, 175-180 ºC/0.10 mmHg. The product was
crystallized from methanol (2×300 mL) to obtain 21.44 g (51%) of white solid which was taken for
the next step without purification.
b)
4

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To a stirred solution of previously obtained product (21.44 g, 51.2 mmol) in
dichloromethane (250 mL), cooled to –78 ºC, boron tribromide (3.6 M in dichloromethane, 43 mL,
155 mmol) was added dropwise. Cooling bath was removed and the mixture was stirred at room
temperature for 18 h. It was cooled with ice/water bath and quenched with cold water (100 mL).
The mixture was stirred for 2 h, poured into water (200 mL) and dichloromethane was evaporated
under reduced pressure. White solid was filtrated, rinsed with water and air-dried to achieve 18.21 g
1
(
91%) of white flaky product, mp=101.5-102 ºC. H NMR (400 MHz, CDCl ) δ [ppm]: 0.86 (t,
3
J=6.9 Hz, 6H, 2CH ), 1.24 (m, 28H, 14CH ), 1.55 (m, 4H, 2CH ), 2.48 (t, J=7.7 Hz, 4H, 2CH ),
3
2
2
2
1
3
4
.23 (s, 2H, 2OH), 6.52 (s, 2H, 2CH ). C NMR (100 MHz, CDCl ) δ [ppm]: 14.11 (2CH ), 22.68
Ar 3 3
(
2CH ), 29.33 (2CH ), 29.54 (2CH ), 29.61 (2CH ), 29.63 (2CH ), 29.66 (2CH ), 29.70 (2CH ),
2
2
2
2
2
2
2
2
9.83 (2CH ), 31.91 (2CH ), 116.67 (2CH ), 126.94 (2C ), 147.07 (2C -OH). IR (ATR) ν
2 2 Ar Ar Ar max
-1
cm : 3392(w), 3339(w), 2954(m), 2918(s), 2850(m), 1494(m), 1465(m), 1333(m), 1239(m),
1
229(m), 1208(m), 1147(s), 875(m), 857(m), 826(m), 724(m). Anal. Calcd. for C H O : C, 79.94;
26 46 2
H, 11.87. Found: C, 80.06; H, 11.84.
2
.2.2. 4,8-Didecyl-2,3,6,7-tetraphenylbenzo[1,2-b:4,5-b']difuran (4)
In a 25 mL round bottom flask equipped with a magnetic stirring bar 2-chloro-1,2-
diphenylethanone (2.31 g, 10 mmol), 2,5-didecylbenzene-1,4-diol (1.95 g, 5 mmol) and zinc
chloride (1.70 g, 12.5 mmol) were plugged with a glass bubbler and heated to 180 ºC under argon
atmosphere. The molten reaction mixture was stirred at this temperature for 15 min. The mixture
was cooled to about 80 ºC and an acetone/ methanol mixture (15 mL, 2:1) was carefully added.
When the reaction mixture was cooled to room temperature, it was filtered on a Schott funnel,
washed with acetone/ methanol mixture (2×10 mL 1:1) and dried to obtain 2.58 g (49%) of olive
1
colored powder. The H NMR analysis showed desired product and traces of benzil, mp=155-157
ºC. 1H NMR (400 MHz, CDCl ) δ [ppm]: 0.87 (t, J=6.8 Hz, 6H, 2CH ), 0.96-1.05 (m, 4H, 2CH ),
3
3
2
1
.07-1.14 (m, 4H, 2CH ), 1.14-1.33 (m, 20H, 10CH ), 1.38-1.48 (m, 4H, 2CH ), 2.63-2.68 (m, 4H,
2 2 2
5

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1
3
2
CH ), 7.20 (m, 6H, 6CH ), 7.48 (m, 14H, 14CH ). C NMR (CDCl , 100MHz), δ ppm: 14.13
2 Ar Ar 3
(
2CH ), 22.71 (2CH ), 25.49 (2CH ), 29.30 (2CH ), 29.37 (2CH ), 29.60 (2CH ), 29.64 (2CH ),
3 2 2 2 2 2 2
2
9.84 (2CH ), 30.91 (2CH ), 31.96 (2CH ), 116.11 (2C ), 118.65 (2C ), 125.85 (2C ), 126.33
2 2 2 Ar Ar Ar
(
4CH ), 127.68 (2CH ), 127.90 (2CH ), 128.25 (4CH ), 128.79 (4CH ), 130.79 (4CH ),
Ar Ar Ar Ar Ar Ar
-
1
1
2
7
8
31.25 (2C ), 134.94 (2C ), 149.70 (2C ), 150.35 (2C ). IR (ATR) ν cm : 2954(m), 2921(m),
Ar Ar Ar Ar max
851(m), 1442(m), 1387(w), 1349(w), 1257(w), 1220(w), 1096(m), 1029(m), 985(m), 769(m),
44(m), 729(m), 700(s), 689(s), 681(s), 670(m), 495(m). Anal. Calcd. for C H O : C, 87.28; H,
54
62
2
.41. Found: C, 87.40; H, 8.38.
2.2.3.1,2-Bis(4-bromophenyl)-2-hydroxyethanone (5)
To a stirred solution of 4-bromobenzaldehyde (48.10 g, 260 mmol) in 60 mL of
water/methanol (2:3) mixture, sodium cyanide (CAUTION: poison) (2.45 g, 50 mmol) was added
in one portion. The mixture was stirred under reflux for 30 min and cooled to rt. The precipitate that
formed was filtered off, washed with water (2×30 mL) and crystallized from methanol/water (19/1)
1
to give 43.69 g (90%) of light yellow solid, mp=96-98 °C. Lit. [43] 94-96 ºC. H NMR (CDCl , 700
3
MHz), δ ppm: 4.47 (d, J=5.8 Hz, 1H, OH), 5.85 (d, J=5.8 Hz, 1H, CH), 7.15-7.17 (m, 2H, 2CHAr),
1
3
7
1
.42-7.44 (m, 2H, 2CH ), 7.52-7.54 (m, 2H, 2CH ), 7.70-7.73 (m, 2H, 2CH ). C NMR (CDCl ,
Ar Ar Ar 3
25 MHz), δ ppm: 76.54 (CH), 123.99 (C ), 130.37 (2CH ), 130.56 (C ), 131.48 (2CH ), 132.93
Ar
Ar
Ar
Ar
-1
(
C ), 133.22 (2CH ), 133.42 (2CH ), 138.63 (C ), 198.63 (C=O). IR (ATR) ν cm : 3445(w),
Ar Ar Ar Ar max
3
1
7
401(w), 1687(m), 1673(s), 1584(m), 1485(m), 1396(m), 1315(w), 1251(m), 1207(m), 1175(m),
110(w), 1084(m), 1070(s), 1011(m), 974(s), 869(m), 844(m), 805(s), 760(w), 743(m), 735(m),
11(w), 684(w), 638(m), 618(m), 568(m), 528(s), 463(m).
2
.2.4. 1,2-Bis(4-bromophenyl)-2-chloroethanone (6)
Cyanuric chloride (18.40 g, 47.3 mmol) and N,N-dimethylformamide (40 mL) were placed
in a 500 mL round bottom flask and stirred at rt for 1 h. Dichloromethane (250 mL) and 1,2-bis(4-
bromophenyl)-2-hydroxyethanone (43.69 g, 118.1 mmol) were added and the mixture was stirred at
6

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rt for 22 h. Water (200 mL) was added and the layers were separated. The aquous layer was
extracted with dichloromethane (2×60 mL), combined organic layers were washed with saturated
sodium carbonate (150 mL), 1M HCl (150 mL), water (2×150 mL), brine (100 mL), and dried over
anhydrous magnesium sulfate. Solvent was removed on rotary evaporator to give 40.24 g (88%) of
1
light yellow solid, mp=81-83 °C. H NMR (CDCl , 400 MHz), δ ppm: 6.18 (s, 1H, CH), 7.33-7.36
3
(
m, 2H, 2CH ), 7.52-7.55 (m, 2H, 2CH ), 7.59-7.63 (m, 2H, 2CH ), 7.80-7.84 (m, 2H, 2CH ).
Ar Ar Ar Ar
1
3
C NMR (CDCl , 100 MHz), δ ppm: 61.77 (CH), 124.67 (C ), 130.34 (2C ), 131.06 (2CH ),
3
Ar
Ar
Ar
1
31.58 (2CH ), 133.24 (2CH ), 133.35 (2CH ), 133.75 (C ), 135.44 (C ), 191.20 (C=O). IR
Ar Ar Ar Ar Ar
-1
(
ATR) νmax cm : 2943(w), 1910(w), 1688(s), 1584(s), 1566(m), 1485(m), 1395(m), 1314(w),
1
7
4
275(w), 1204(m), 1171(m), 1103(w), 1070(s), 1010(s), 997(m), 859(m), 832(m), 800(s), 761(s),
30(s), 710(m), 689(w), 665(m), 628(w), 586(w), 507(s), 462(m). Anal. Calcd. for C H Br ClO: C,
1
4
9
2
3.28; H, 2.34. Found: C, 43.13; H, 2.31.
2
.2.5. 2,3,6,7-Tetrakis(4-bromophenyl)-4,8-didecylbenzo[1,2-b:4,5-b']difuran (7)
The mixture of 1,2-bis(4-bromophenyl)-2-chloroethanone (20.17 g, 52 mmol), 2,5-
didecylbenzene-1,4-diol (8.45 g, 21.6 mmol), and zinc dichloride (13.54 g, 99.4 mmol) was
immersed in an oil bath preheated to 180 °C and stirred under argon for 15 min. It was cooled to
about 80 ºC and acetone/methanol mixture (65 mL, 2:1) was added. When the reaction mixture was
cooled to rt, precipitate was filtered off on a Schott funnel, washed with acetone/methanol mixture
(1:1, 250 mL) and dried to give 11.64 g of beige colored powder.
The crude product was dissolved in tetrahydrofuran (50 mL) at 0 ºC, 30% hydrogen dioxide
1.9 mL) and 10% sodium hydroxide (6.6 mL) were added. The cooling bath was removed and the
(
reaction mixture was stirred at room temperature for 1 h. Precipitate was filtered off, washed with
10% sodium hydroxide (20 mL), water (20 mL) and air-dried to give 9.55 g (44%) of ivory powder,
1
mp=205-207 °C. H NMR (CDCl , 400 MHz), δ ppm: 0.87 (t, J=6.7 Hz, 6H, 2CH ), 0.99-1.05 (m,
3
3
4
H, 2CH ), 1.06-1.13 (m, 4H, 2CH ), 1.15-1.31 (m, 20H, 10CH ), 1.34-1.43 (m, 4H, 2CH ), 2.62-
2 2 2 2
7

ACCEPTED MANUSCRIPT
2
.67 (m, 4H, 2CH ), 7.28-7.31 (m, 4H, 4CH ), 7.32-7.36 (m, 4H, 4CH ), 7.37-7.40 (m, 4H,
2 Ar Ar
1
3
4
CH ), 7.61-7.64 (m, 4H, 4CH ). C NMR (CDCl , 125MHz), δ ppm: 14.14 (2CH ), 22.72
Ar
Ar
3
3
(
2CH ), 25.47 (2CH ), 29.33 (2CH ), 29.42 (2CH ), 29.65 (4CH ), 29.82 (2CH ), 30.92 (2CH ),
2 2 2 2 2 2 2
3
1.94 (2CH ), 116.19 (2C ), 117.81 (2C ), 122.26 (2C ), 122.43 (2C ), 125.65 (2C ), 127.82
2 Ar Ar Ar Ar Ar
(
4CH ), 129.63 (2C ), 131.65 (4CH ), 132.21 (4CH ), 132.32 (4CH ), 133.44 (2C ), 149.75
Ar
Ar
Ar
Ar
Ar
Ar
-1
(
2C ), 149.81 (2C ). IR (ATR) ν
cm : 2918(m), 2849(m), 1579(w), 1491(m), 1389(m),
max
Ar
Ar
1341(m), 1252(m), 1164(w), 1128(w), 1096(m), 1069(s), 1007(s), 985(m), 928(w), 825(s), 765(w),
7
40(m), 722(w), 706(w), 678(w), 623(w), 579(w), 505(m). Anal. Calcd. for C H Br O : C, 61.26;
54
58
4
2
H, 5.52. Found: C, 61.42; H, 5.57.
2.2.6. General procedure for tetrasubstituted benzodifurans (8-22)
To a stirred solution of 2,3,6,7-tetrakis(4-bromophenyl)-4,8-didecylbenzo[1,2-b:4,5-
b']difuran (7) (0.318 g, 0.3 mmol), an appropriate boronic acid MIDA ester (1.8 mmol), and [1,1′-
bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.066 g, 0.09 mmol), an argon degassed
1,4-dioxane (6 mL) was added. The resulting mixture was stirred at room temperature for 5 min.
under argon atmosphere. Tripotassium phosphate (3 M aqueous solution, 1.2 mL) was added and
the mixture was stirred at 80 ºC for 22 h. Reaction mixture was cooled to rt and transferred into a
separatory funnel. Chloroform (50 mL) and 10% sodium hydroxide (10 mL) were added and the
layers were separated. Aquous layer was extracted with chloroform (3×50 mL). Combined organic
layers were dried over anhydrous magnesium sulfate and concentrated. The crude product was
crystallized from chloroform/methanol or p-xylene.
2
.2.6.1. 2,3,6,7-Tetra([1,1'-biphenyl]-4-yl)-4,8-didecylbenzo[1,2-b:4,5-b']difuran (8)
Prepared from phenylboronic acid MIDA ester, 0.288 g (92%) of grey solid, mp=235-237
ºC. H NMR (CDCl , 700 MHz), δ ppm: 0.88 (t, J=7.0 Hz, 6H, 2CH ), 1.04-1.10 (m, 4H, 2CH ),
1
3
3
2
1
2
.12-1.21 (m, 20H, 10CH ), 1.22-1.30 (m, 4H, 2CH ), 1.48-1.54 (m, 4H, 2CH ), 2.78-2.80 (m, 4H,
2 2 2
CH ), 7.31-7.37 (m, 2H, 2CH ), 7.40-7.45 (m, 6H, 6CH ), 7.51-7.56 (m, 8H, 8CH ), 7.57-7.61
2
Ar
Ar
Ar
8

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(
m, 4H, 4CH ), 7.64-7.67 (m, 8H, 8CH ), 7.76-7.79 (m, 4H, 4CH ), 7.80-7.82 (m, 4H, 4CH ).
Ar Ar Ar Ar
1
3
C NMR (CDCl , 125 MHz), δ ppm: 14.13 (2CH ), 22.671 (2CH ), 25.62 (2CH ), 29.38 (2CH ),
3
3
2
2
2
2
9.42 (2CH ), 29.66 (2CH ), 29.70 (2CH ), 29.97 (2CH ), 31.02 (2CH ), 31.91 (2CH ), 116.14
2 2 2 2 2 2
(
2C ), 118.47 (2C ), 126.01 (2C ), 126.70 (4CH ), 126.88 (4CH ), 126.98 (4CH ), 127.08
Ar Ar Ar Ar Ar Ar
(
4CH ), 127.340 (2CH ), 127.45 (4CH ), 127.52 (2CH ), 128.78 (4CH ), 128.90 (4CH ),
Ar Ar Ar Ar Ar Ar
1
30.15 (2C ), 131.24 (4CH ), 133.91 (2C ), 140.30 (2C ), 140.46 (2C ), 140.66 (2C ), 140.69
Ar Ar Ar Ar Ar Ar
-1
(
2C ), 149.84 (2C ), 150.28 (2C ). IR (ATR) ν cm : 2919(m), 2850(m), 1598(w), 1484(m),
Ar Ar Ar max
1
5
388(w), 1345(w), 1224(w), 1097(m), 1011(m), 840(s), 763(s), 746(s), 739(m), 720(m), 691(s),
78(w), 551(w). Anal. Calcd. for C H O : C, 89.44; H, 7.51. Found: C, 89.52; H, 7.52.
7
8
78
2
2
.2.6.2. 4,8-Didecyl-2,3,6,7-tetrakis(4'-methoxy-[1,1'-biphenyl]-4-yl)benzo[1,2-b:4,5-
b']difuran (9)
Prepared from 4-methoxyphenylboronic acid MIDA ester, 0.405 g (99%) of dark green
1
solid, mp=287-289 °C. H NMR (CDCl , 400 MHz), δ ppm: 0.86 (t, J=6.8 Hz, 6H, 2CH ), 1.03-
3
3
1
.29 (m, 28H, 14CH ), 1.46-1.55 (m, 4H, 2CH ), 2.75-2.79 (m, 4H, 2CH ), 3.83 (s, 6H, 2CH ), 3.90
2 2 2 3
(
s, 6H, 2CH ), 6.93-6.96 (m, 4H, 4CH ), 7.04-7.06 (m, 4H, 4CH ), 7.45-7.51 (m, 8H, 8CH ),
3 Ar Ar Ar
1
3
7
.57-7.62 (m, 8H, 8CH ), 7.68-7.74 (m, 8H, 8CH ). C NMR (CDCl , 100 MHz), δ ppm: 14.12
Ar Ar 3
(
2CH ), 22.71 (2CH ), 25.60 (2CH ), 29.37 (2CH ), 29.43 (2CH ), 29.66 (2CH ), 29.70 (2CH ),
3 2 2 2 2 2 2
2
9.97 (2CH ), 31.01 (2CH ), 31.92 (2CH ), 55.39 (2CH ), 55.33 (2CH ), 114.25 (4CH ), 114.34
2 2 2 3 3 Ar
(
(
(
4CH ), 116.06 (2C ), 118.31 (2C ), 126.00 (2C ), 126.45 (4CH ), 126.68 (4CH ), 126.94
Ar Ar Ar Ar Ar Ar
4CH ), 127.89 (4CH ), 128.08 (4CH ), 129.58 (2C ), 131.20 (4CH ), 133.01 (2C ), 133.27
Ar
Ar
Ar
Ar
Ar
Ar
4C ), 139.87 (2C ), 140.17 (2C ), 149.80 (2C ), 150.32 (2C ), 159.28 (2C ), 159.36 (2C ).
Ar
Ar
Ar
Ar
Ar
Ar
Ar
-1
IR (ATR) νmax cm : 2933(m), 1607(m), 1500(m), 1488(m), 1465(w), 1441(w), 1389(w), 1289(m),
1
6
7
250(s), 1177(s), 1074(s), 1038(s), 1014(m), 1000(m), 852(w), 824(s), 807(m), 748(w), 719(m),
78(w), 609(m), 572(m), 515(m). Anal. Calcd. for C H O : C, 84.35; H, 7.42. Found: C, 84.24; H,
8
2
86
6
.46.
9

ACCEPTED MANUSCRIPT
2
.2.6.3. 4,8-Didecyl-2,3,6,7-tetrakis(2'-methoxy-[1,1'-biphenyl]-4-yl)benzo[1,2-b:4,5-
b']difuran (10)
Prepared from 2-methoxyphenylboronic acid MIDA ester, 0.326 g (93%) of green-grey
1
solid, mp=170-171 °C. H NMR (CDCl , 400 MHz), δ ppm: 0.84 (t, J=6.8 Hz, 6H, 2CH ), 1.08-
3
3
1
2
7
4
1
.15 (m, 4H, 2CH ), 1.16-1.23 (m, 20H, 10CH ), 1.23-1.28 (m, 4H, 2CH ), 1.49-1.57 (m, 4H,
2 2 2
CH ), 2.74-2.79 (m, 4H, 2CH ), 3.81 (s, 6H, 2CH ), 3.88 (s, 6H, 2CH ), 6.96-7.11 (m, 8H, 8CH ),
2
2
3
3
Ar
.28-7.32 (m, 4H, 4CH ), 7.35-7.39 (m, 2H, 2CH ), 7.45-7.49 (m, 6H, 6CH ), 7.57-7.59 (m, 4H,
Ar
Ar
Ar
1
3
CH ), 7.64-7.66 (m, 4H, 4CH ), 7.70-7.72 (m, 4H, 4CH ). C NMR (CDCl , 100 MHz), δ ppm:
Ar
Ar
Ar
3
4.12 (2CH ), 22.71 (2CH ), 25.66 (2CH ), 29.44 (4CH ), 29.64 (2CH ), 29.69 (2CH ), 29.91
3
2
2
2
2
2
(
(
(
(
(
2CH ), 31.04 (2CH ), 31.92 (2CH ), 55.54 (2CH ), 55.66 (2CH ), 111.25 (2CH ), 111.62
2 2 2 3 3 Ar
2CH ), 116.14 (2C ), 118.57 (2C ), 120.87 (2CH ), 120.97 (2CH ), 125.98 (4CH ), 126.11
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 128.68 (2CH ), 128.74 (2CH ), 129.46 (4CH ), 129.91 (4CH ), 129.93 (2C ), 130.21
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 130.39 (4CH ), 130.51 (2C ), 130.70 (2CH ), 130.94 (2CH ), 133.37 (2C ), 137.84
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 138.12 (2C ), 149.78 (2C ), 150.36 (2C ), 156.56 (2C ), 156.74 (2C ). IR (ATR) ν
Ar
Ar
Ar
Ar
Ar
Ar
max
-1
cm : 3671(w), 2962(m), 2916(m), 1589(w), 1482(m), 1455(m), 1434(w), 1393(w), 1258(s),
1
4
179(w), 1079(s), 1056(s), 1023(s), 1004(s), 839(m), 798(s), 751(s), 733(m), 682(m), 565(w),
78(w). Anal. Calcd. for C H O : C, 84.35; H, 7.42. Found: C, 84.52; H, 7.39.
82
86
6
2
.2.6.4. 4,8-Didecyl-2,3,6,7-tetrakis(3'-methoxy-[1,1'-biphenyl]-4-yl)benzo[1,2-b:4,5-
b']difuran (11)
Prepared from 3-methoxyphenylboronic acid MIDA ester, 0.168 g (48%) of green-grey
1
solid, mp=257.5-259 °C. H NMR (CDCl , 400 MHz), δ ppm: 0.85 (t, J=7.2 Hz, 6H, 2CH ), 1.02-
3
3
1
.31 (m, 28H, 14CH ), 1.46-1.54 (m, 4H, 2CH ), 2.75-2.79 (m, 4H, 2CH ), 3.84 (s, 6H, 2CH ), 3.93
2 2 2 3
(
s, 6H, 2CH ), 6.86-6.90 (m, 2H, 2CH ), 6.95-6.98 (m, 2H, 2CH ), 7.09-7.10 (m, 2H, 2CH ),
3 Ar Ar Ar
7
2
.14-7.17 (m, 2H, 2CH ), 7.28-7.30 (m, 2H, 2CH ), 7.31-7.33 (m, 2H, 2CH ), 7.33-7.36 (m, 2H,
Ar Ar Ar
CH ), 7.40-7.46 (m, 2H, 2CH ), 7.49-7.52 (m, 4H, 4CH ), 7.61-7.64 (m, 8H, 8CH ), 7.77-7.79
Ar
Ar
Ar
Ar
1
0

ACCEPTED MANUSCRIPT
1
3
(
m, 4H, 4CH ). C NMR (CDCl , 100 MHz), δ ppm: 14.12 (2CH ), 22.72 (2CH ), 25.64 (2CH ),
Ar 3 3 2 2
2
9.40 (2CH ), 29.43 (2CH ), 29.67 (2CH ), 29.72 (2CH ), 29.97 (2CH ), 31.02 (2CH ), 31.91
2 2 2 2 2 2
(
2CH ), 55.28 (2CH ), 55.36 (2CH ), 112.46 (2CH ), 112.86 (2CH ), 112.94 (2CH ), 113.03
2 3 3 Ar Ar Ar
(
2CH ), 116.17 (2C ), 118.49 (2C ), 119.40 (2CH ), 119.61 (2CH ), 126.02 (2C ), 126.69
Ar Ar Ar Ar Ar Ar
(
4CH ), 127.03 (4CH ), 127.50 (4CH ), 129.78 (2CH ), 129.91 (2CH ), 130.29 (2C ), 131.22
Ar Ar Ar Ar Ar Ar
(
4CH ), 134.08 (2C ), 140.19 (2C ), 140.54 (2CH ), 141.98 (2C ), 142.20 (2C ), 149.87
Ar Ar Ar Ar Ar Ar
-1
(
2C ), 150.28 (2C ), 159.99 (2C ), 160.14 (2C ). IR (ATR) ν
cm : 3671(w), 2956(m),
max
Ar
Ar
Ar
Ar
2
1
9
923(m), 2854(m), 1598(m), 1579(m), 1551(w), 1522(w), 1478(m), 1454(m), 1432(m), 1394(m),
342(w), 1293(m), 1259(m), 1213(s), 1169(m), 1091(m), 1052(s), 1032(s), 1014(s), 994(m),
26(w), 877(m), 866(m), 836(s), 779(s), 747(m), 724(m), 694(m), 654(w), 627(w), 566(m), 532(m).
Anal. Calcd. for C H O : C, 84.35; H, 7.42. Found: C, 84.48; H, 7.37.
8
2
86
6
2
.2.6.5. ((4,8-Didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-tetrayl)tetrakis([1,1'-biphenyl]-
',4-diyl))tetramethanol (12)
4
Prepared from 4-(hydroxymethyl)phenylboronic acid MIDA ester, crystallized from
1
chloroform/methanol, 0.129 g (37%) of yellow solid, mp>530 °C. H NMR (CDCl , 400 MHz), δ
3
ppm: 0.85 (t, J=6.8 Hz, 6H, 2CH ), 0.99-1.32 (m, 32H, 16CH ), 2.73-2.80 (m, 4H, 2CH ), 4.73 (s,
3
2
2
4
H, 2CH ), 4.80 (s, 4H, 2CH ), 7.41 (d, J=8.2 Hz, 4H, 4CH ), 7.50-7.53 (m, 8H, 8CH ), 7.57 (d,
2 2 Ar Ar
J=8.2 Hz, 4H, 4CH ), 7.61-7.65 (m, 8H, 8CH ), 7.75 (d, J=8.2 Hz, 4H, 4CH ), 7.78 (d, J=8.2 Hz,
Ar
Ar
Ar
4
H, 4CH ). Protons of the hydroxyl groups are not visible due to low solubility in deuterated
Ar
1
3
-1
solvent and exchange with residual D O. Solubility too low for C NMR. IR (ATR) ν
cm :
max
2
3365(w), 2921(s), 2852(m), 1500(w), 1487(m), 1459(w), 1391(m), 1254(w), 1215(w), 1048(s),
1
004(s), 810(s), 745(w), 720(m), 627(w), 519(m). Anal. Calcd. for C H O : C, 84.35; H, 7.42.
8
2
86
6
Found: C, 84.12; H, 7.47.
2
.2.6.6. 4',4''',4''''',4'''''''-(4,8-Didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-
tetrayl)tetrakis([1,1'-biphenyl]-4-carbonitrile) (13)
1
1

ACCEPTED MANUSCRIPT
Prepared from 4-cyanophenylboronic acid MIDA ester, crystallized from p-xylene, 0.137 g
1
(
40%) of dark green solid, mp=347.5-349.5 °C. H NMR (CDCl , 700 MHz), δ ppm: 0.86 (t, J=7.0
3
Hz, 6H, 2CH ), 1.01-1.28 (m, 28H, 14CH ), 1.46-1.51 (m, 4H, 2CH ), 2.75-2.77 (m, 4H, 2CH ),
3
2
2
2
7
8
.51-7.53 (m, 4H, 4CH ), 7.63-7.66 (m, 8H, 8CH ), 7.67-7.71 (m, 8H, 8CH ), 7.80-7.82 (m, 8H,
Ar Ar Ar
1
3
CH ), 7.84-7.86 (m, 4H, 4CH ). C NMR (CDCl , 125MHz), δ ppm: 14.13 (2CH ), 22.69
Ar
Ar
3
3
(
2CH ), 25.63 (2CH ), 29.32 (2CH ), 29.41 (2CH ), 29.65 (2CH ), 29.70 (2CH ), 29.94 (2CH ),
2 2 2 2 2 2 2
3
0.97 (2CH ), 31.92 (2CH ), 111.13 (2C ), 111.42 (2C ), 116.30 (2C ), 118.68 (2C ), 118.80
2 2 Ar Ar Ar Ar
(
(
(
2C ), 126.05 (2C ), 126.96 (4CH ), 127.20 (4CH ), 127.37 (4CH ), 127.65 (8CH ), 128.90
Ar Ar Ar Ar Ar Ar
2C ), 130.55 (2C ), 131.21 (2C ), 131.59 (4CH ), 132.66 (4CH ), 132.78 (4CH ), 135.29
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 138.34 (2C ), 144.69 (2C ), 144.92 (2C ), 149.97 (2C ), 150.10 (2C ). IR (ATR) ν
Ar
Ar
Ar
Ar
Ar
Ar
max
-1
cm : 3672(w), 2964(m), 2920(m), 2851(m), 2222(w), 1603(m), 1492(w), 1461(w), 1390(w),
1348(w), 1286(w), 1253(w), 1179(w), 1132(w), 1065(m), 1004(m), 930(w), 856(w), 822(s),
7
65(w), 747(w), 720(w), 677(w), 628(w), 562(m), 530(m), 485(w). Anal. Calcd. for C H N O :
8
2
74
4
2
C, 85.83; H, 6.50; N, 4.88. Found: C, 85.39; H, 6.44; N, 4.96.
2
.2.6.7. 4',4''',4''''',4'''''''-(4,8-Didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-
tetrayl)tetrakis([1,1'-biphenyl]-4-carbaldehyde) (14)
Prepared from 4-formylphenylboronic acid MIDA ester, crystallized from
1
chloroform/methanol, 0.213 g (61%) of yellow solid, mp=326-328 °C. H NMR (CDCl , 400
3
MHz), δ ppm: 0.84 (t, J=6.8 Hz, 6H, 2CH ), 1.03-1.30 (m, 28H, 14CH ), 1.45-1.53 (m, 4H, 2CH ),
3
2
2
2
4
2
.76-2.80 (m, 4H, 2CH ), 7.56-7.59 (m, 4H, 4CH ), 7.65-7.70 (m, 8H, 8CH ), 7.71-7.74 (m, 4H,
2 Ar Ar
CH ), 7.85-7.87 (m, 4H, 4CH ), 7.91-7.94 (m, 8H, 8CH ), 8.03-8.05 (m, 4H, 4CH ), 10.03 (s,
Ar
Ar
Ar
Ar
1
3
H, 2CHO), 10.12 (s, 2H, 2CHO). C NMR (CDCl , 100 MHz), δ ppm: 15.09 (2CH ), 23.66
3
3
(
2CH ), 26.65 (2CH ), 30.32 (2CH ), 30.38 (2CH ), 30.62 (2CH ), 30.68 (2CH ), 30.94 (2CH ),
2 2 2 2 2 2 2
3
1.98 (2CH ), 32.89 (2CH ), 117.29 (2C ), 119.74 (2C ), 127.05 (2C ), 127.90 (4CH ), 128.32
2 2 Ar Ar Ar Ar
(
4CH ), 128.34 (4CH ), 128.62 (4CH ), 128.80 (4CH ), 131.29 (4CH ), 131.40 (4CH ),
Ar Ar Ar Ar Ar Ar
1
2

ACCEPTED MANUSCRIPT
1
32.10 (2C ), 132.49 (4CH ), 136.14 (2C ), 136.34 (2C ), 136.53 (2C ), 139.86 (2C ), 140.38
Ar Ar Ar Ar Ar Ar
(2C ), 147.23 (2C ), 147.47 (2C ), 150.99 (2C ), 151.15 (2C ), 192.70 (2CHO), 192.75
Ar Ar Ar Ar Ar
-1
(
2CHO). IR (ATR) νmax cm : 3671(w), 2923(m), 2853(w), 1697(s), 1601(s), 1574(w), 1525(w),
1
8
8
460(w), 1384(m), 1349(w), 1307(w), 1212(m), 1168(m), 1134(m), 1074(m), 1004(m), 926(w),
37(m), 819(s), 773(w), 747(w), 679(w), 664(w), 627(w), 500(w). Anal. Calcd. for C H O : C,
8
2
78
6
4.94; H, 6.78. Found: C, 85.10; H, 7.81.
2
.2.6.8. Tetramethyl 4',4''',4''''',4'''''''-(4,8-didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-
tetrayl)tetrakis([1,1'-biphenyl]-3-carboxylate) (15)
Prepared from 3-methoxycarbonylphenylboronic acid MIDA ester, crystallized from
1
chloroform/methanol, 0.188 g (49%) of orange solid, mp=227.5-229 °C. H NMR (CDCl , 400
3
MHz), δ ppm: 0.83 (t, J=6.8 Hz, 6H, 2CH ), 1.06-1.26 (m, 28H, 14CH ), 1.48-1.52 (m, 4H, 2CH ),
3
2
2
2
7
2
.77-2.81 (m, 4H, 2CH ), 3.92 (s, 6H, 2CH ), 3.99 (s, 6H, 2CH ), 7.47-7.51 (m, 2H, 2CH ), 7.55-
2 3 3 Ar
.58 (m, 4H, 4CH ), 7.60-7.62 (m, 2H, 2CH ), 7.64-7.67 (m, 8H, 8CH ), 7.76-7.78 (m, 2H,
Ar
Ar
Ar
CH ), 7.82-7.84 (m, 4H, 4CH ), 7.94-7.96 (m, 2H, 2CH ), 7.98-8.00 (m, 2H, 2CH ), 8.08-8.10
Ar
Ar
Ar
Ar
1
3
(
m, 2H, 2CH ), 8.25-8.26 (m, 2H, 2CH ), 8.44-8.45 (m, 2H, 2CH ). C NMR (CDCl , 100
Ar Ar Ar 3
MHz), δ ppm: 14.09 (2CH ), 22.68 (2CH ), 25.64 (2CH ), 29.36 (2CH ), 29.39 (2CH ), 29.63
3
2
2
2
2
(
2CH ), 29.69 (2CH ), 29.97 (2CH ), 31.01 (2CH ), 31.88 (2CH ), 52.17 (2CH ), 52.25 (2CH ),
2 2 2 2 2 3 3
1
16.21 (2C), 118.55 (2C), 126.02 (2C ), 126.83 (4CH ), 127.02 (4CH ), 127.57 (4CH ), 127.98
Ar Ar Ar Ar
(
2CH ), 128.25 (2CH ), 128.51 (2CH ), 128.64 (2CH ), 128.90 (2CH ), 129.02 (2CH ),
Ar Ar Ar Ar Ar Ar
1
1
30.53 (2C), 130.78 (2C ), 130.89 (2C ), 131.55 (2CH ), 131.49 (4CH ), 131.47 (2CH ),
Ar Ar Ar Ar Ar
34.43 (2C ), 139.20 (2C ), 139.71 (2C ), 140.65 (2C ), 140.96 (2C ), 149.96 (2C ), 150.23
Ar
Ar
Ar
Ar
Ar
Ar
-1
(
2C ), 166.94 (2C ), 167.05 (2C ). IR (ATR) ν
cm : 2922(m), 2854(w), 1724(s), 1584(w),
max
Ar
Ar
Ar
1
7
438(m), 1303(m), 1241(s), 1108(s), 1087(m), 1043(m), 970(w), 843(m), 815(m), 756(m), 742(m),
25(m), 686(m), 513(w). Anal. Calcd. for C H O : C, 80.72; H, 6.77. Found: C, 80.49; H, 6.77.
8
6
86 10
1
3

ACCEPTED MANUSCRIPT
2
.2.6.9. 4,8-Didecyl-2,3,6,7-tetrakis(4-(naphthalen-2-yl)phenyl)benzo[1,2-b:4,5-
b']difuran (16)
Prepared from 2-naphthylboronic acid MIDA ester, crystallized from p-xylene, 0.140 g
1
(
37%) of green solid, mp=287.5-289 °C. H NMR (CDCl , 700 MHz), δ ppm: 0.80 (t, J=7.3 Hz,
3
6
7
2
H, 2CH ), 1.09-1.29 (m, 32H, 16CH ), 2.82-2.84 (m, 4H, 2CH ), 7.45-7.49 (m, 4H, 4CH ), 7.52-
3 2 2 Ar
.56 (m, 4H, 4H ), 7.67-7.74 (m, 14H, 14CH ), 7.83-7.86 (m, 4H, 4CH ), 7.88-7.89 (m, 2H,
Ar
Ar
Ar
CH ), 7.91-7.93 (m, 4H, 4CH ), 7.94-7.95 (m, 4H, 4CH ), 7.96-7.97 (m, 2H, 2CH ), 8.00-8.01
Ar
Ar
Ar
Ar
1
3
(
m, 2H, 2CH ), 8.02-8.04 (m, 2H, 2CH ), 8.21-8.23 (m, 2H, 2CH ). Solubility too low for C
Ar Ar Ar
-1
NMR. IR (ATR) νmax cm : 2920(w), 2850(w), 1597(w), 1498(w), 1131(w), 890(w), 839(m),
8
6
14(s), 751(m), 548(w), 474(s). Anal. Calcd. for C H O : C, 90.49; H, 6.95. Found: C, 90.67; H,
94 86 2
.89.
2
.2.6.10.4,8-Didecyl-2,3,6,7-tetrakis(4-(naphthalen-1-yl)phenyl)benzo[1,2-b:4,5-
b']difuran (17)
Prepared from 2-naphthylboronic acid MIDA ester, crystallized from chloroform/methanol,
1
0
.259 g (69%) dark green solid, mp=247-248 °C. H NMR (CDCl , 400 MHz), δ ppm: 0.82 (t,
3
J=6.8 Hz, 6H, 2CH ), 1.10-1.30 (m, 28H, 14CH ), 1.63-1.72 (m, 4H, 2CH ), 2.92-2.95 (m, 4H,
3
2
2
2
7
4
CH ), 7.42-7.57 (m, 16H, 16CH ), 7.58-7.62 (m, 4H, 4CH ), 7.70-7.74 (m, 4H, 4CH ), 7.76-
2 Ar Ar Ar
.82 (m, 8H, 8CH ), 7.87-7.89 (m, 2H, 2CH ), 7.92-7.95 (m, 4H, 4CH ), 7.96-8.00 (m, 4H,
Ar
Ar
Ar
1
3
CH ), 8.08-8.10 (m, 2H, 2CH ). C NMR (CDCl , 100 MHz), δ ppm: 14.08 (2CH ), 22.66
Ar
Ar
3
3
(
2CH ), 25.82 (2CH ), 29.41 (2CH ), 29.51 (2CH ), 29.67 (2CH ), 29.69 (2CH ), 30.17 (2CH ),
2 2 2 2 2 2 2
3
1.15 (2CH ), 31.86 (2CH ), 116.27 (2C ), 118.67 (2C ), 125.41 (4CH ), 125.87 (6CH ), 125.95
2 2 Ar Ar Ar Ar
(
(
(
(
2CH ), 126.12 (2CH ), 126.17 (2C ), 126.21 (6CH ), 126.91 (2CH ), 127.14 (2CH ), 127.80
Ar Ar Ar Ar Ar Ar
2CH ), 127.89 (2CH ), 128.33 (2CH ), 128.42 (2CH ), 130.16 (4CH ), 130.25 (2C ), 130.64
Ar
Ar
Ar
Ar
Ar
Ar
4CH ), 130.78 (4CH ), 131.47 (2C ), 131.61 (2C ), 133.85 (2C ), 133.93 (4C ), 139.73
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 139.91 (2C ), 140.27 (2C ), 140.52 (2C ), 149.92 (2C ), 150.45 (2C ). IR (ATR) ν
max
Ar
Ar
Ar
Ar
Ar
Ar
1
4

ACCEPTED MANUSCRIPT
-
1
cm : 2919(w), 2850(w), 1590(w), 1492(w), 1454(w), 1389(w), 1132(w), 1091(w), 1020(w),
89(w), 963(w), 846(m), 828(w), 800(s), 776(s), 683(w), 643(w), 625(w), 583(w), 568(m). Anal.
Calcd. for C H O : C, 90.49; H, 6.95. Found: C, 90.72; H, 6.94.
9
9
4
86
2
2
.2.6.11. 4,4',4'',4'''-((4,8-Didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-
tetrayl)tetrakis(benzene-4,1-diyl))tetrapyridine (18)
Prepared from 4-pyridinylboronic acid MIDA ester, crystallized from p-xylene, 0.133 g
1
(
42%) of dark green solid, mp=264.5-266 °C. H NMR (CDCl , 700 MHz), δ ppm: 0.85 (t, J=7.1
3
Hz, 6H, 2CH ), 1.02-1.08 (m, 4H, 2CH ), 1.10-1.20 (m, 20H, 10CH ), 1.22-1.26 (m, 4H, 2CH ),
3
2
2
2
1
4
4
.48-1.52 (m, 4H, 2CH ), 2.75-2.78 (m, 4H, 2CH ), 7.47-7.48 (m, 4H, 4CH ), 7.57-7.58 (m, 4H,
2 2 Ar
CH ), 7.64-7.70 (m, 12H, 12CH ), 7.85-7.86 (m, 4H, 4CH ), 8.64 (s, 4H, 4CH ), 8.75 (s, 4H,
Ar
Ar
Ar
Ar
1
3
CH ). C NMR (CDCl , 100 MHz), δ ppm: 14.12 (2CH ), 22.69 (2CH ), 25.65 (2CH ), 29.33
Ar
3
3
2
2
(
2CH ), 29.39 (2CH ), 29.65 (2CH ), 29.69 (2CH ), 29.93 (2CH ), 30.98 (2CH ), 31.89 (2CH ),
2 2 2 2 2 2 2
1
1
1
16.33 (2C ), 118.77 (2C ), 121.20 (4CH ), 121.49 (4CH ), 126.01 (2C ), 126.97 (8CH ),
Ar Ar Ar Ar Ar Ar
27.47 (4CH ), 131.58 (4CH ), 131.61 (2C ), 135.73 (2C ), 137.31 (2C ), 137.86 (2C ),
Ar
Ar
Ar
Ar
Ar
Ar
47.35 (2C ), 147.60 (2C ), 149.98 (2C ), 150.07 (2C ), 150.37 (4CH ), 150.51 (4CH ). IR
Ar
Ar
Ar
Ar
Ar
Ar
-1
(
ATR) νmax cm : 3669(w), 2987(w), 2931(m), 2852(w), 1594(m), 1488(w), 1485(w), 1398(w),
1226(w), 1067(m), 993(m), 857(m), 814(s), 754(m), 735(m), 679(w), 645(w), 566(m), 518(m),
4
98(m), 472(w). Anal. Calcd. for C H N O : C, 84.53; H, 7.09; N, 5.33. Found: C, 84.26; H, 7.07;
7
4
74
4
2
N, 5.41.
2
.2.6.12. 3,3',3'',3'''-((4,8-Didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-
tetrayl)tetrakis(benzene-4,1-diyl))tetraquinoline (19)
Prepared from 3-quinolineboronic acid MIDA ester, crystallized from chloroform/methanol,
1
0
.412 g (99%) of green solid, mp=287-289 °C. H NMR (CDCl , 400 MHz), δ ppm: 0.78 (t, J=6.8
3
Hz, 6H, 2CH ), 1.00-1.50 (m, 32H, 16CH ), 2.82-2.86 (m, 4H, 2CH ), 7.52-7.80 (m, 20H, 20CH ),
3
2
2
Ar
1
5

ACCEPTED MANUSCRIPT
7
.84-7.86 (m, 2H, 2CH ), 7.95-7.97 (m, 6H, 6CH ), 8.11-8.13 (m, 2H, 2CH ), 8.20-8.22 (m, 2H,
Ar Ar Ar
2
CH ), 8.29-8.30 (m, 2H, 2CH ), 8.49-8.50 (m, 2H, 2CH ), 9.17-9.18 (m, 2H, 2CH ), 9.36-9.37
Ar
Ar
Ar
Ar
1
3
-1
(
m, 2H, 2CH ). Solubility too low for C NMR. IR (ATR) ν cm : 3671(w), 2969(m), 2922(m),
Ar max
2
9
4
852(m), 1604(w), 1492(m), 1470(m), 1384(w), 1343(m), 1259(m), 1074(s), 1017(m), 951(m),
10(w), 867(w), 835(s), 785(s), 753(s), 721(m), 677(m), 620(m), 585(w), 569(w), 551(m), 513(w),
79(w). Anal. Calcd. for C H O : C, 86.36; H, 6.60; N, 4.48. Found: C, 86.47; H, 6.55; N, 4.58.
90
82
2
2
.2.6.13. 4,8-Didecyl-2,3,6,7-tetrakis(4-(furan-3-yl)phenyl)benzo[1,2-b:4,5-b']difuran
20)
(
Prepared from furan-3-boronic acid MIDA ester, crystallized from chloroform/methanol,
1
0
.149 g (49%) of orange solid, mp=224-226 °C. H NMR (CDCl , 700 MHz), δ ppm: 0.87 (t, J=7.0
3
Hz, 6H, 2CH ), 1.05-1.08 (m, 4H, 2CH ), 1.10-1.21 (m, 20H, 10CH ), 1.23-1.28 (m, 4H, 2CH ),
3
2
2
2
1
.46-1.51 (m, 4H, 2CH ), 2.74-2.76 (m, 4H, 2CH ), 6.65-6.66 (m, 2H, CH ), 6.82-6.83 (m, 2H,
2 2 2
CH ), 7.37-7.39 (m, 4H, 4CH ), 7.44-7.45 (m, 2H, 2CH ), 7.53-7.56 (m, 10H, 10CH ), 7.64-7.66
2
Ar
Ar
Ar
1
3
(
m, 4H, 4CH ), 7.70 (s, 2H, 2CH ), 7.87 (s, 2H, 2CH ). C NMR (CDCl , 100 MHz), δ ppm:
Ar Ar Ar 3
1
4.13 (2CH ), 22.71 (2CH ), 25.53 (2CH ), 29.36 (2CH ), 29.42 (2CH ), 29.65 (2CH ), 29.69
3 2 2 2 2 2
(
(
(
(
(
2CH ), 29.89 (2CH ), 30.96 (2CH ), 31.91 (2CH ), 108.59 (2CH ), 108.77 (2CH ), 116.04
2 2 2 2 Ar Ar
2C ), 118.24 (2C ), 125.67 (4CH ), 125.90 (2C ), 126.03 (2C ), 126.19 (4CH ), 126.21
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 126.70 (4CH ), 129.77 (2C ), 131.25 (4CH ), 131.69 (2C ), 131.99 (2C ), 133.55
Ar
Ar
Ar
Ar
Ar
Ar
2C ), 138.67 (2CH ), 138.74 (2CH ), 143.76 (2CH ), 143.87 (2CH ), 149.76 (2C ), 150.30
Ar
Ar
Ar
Ar
Ar
Ar
-1
2C ). IR (ATR) νmax cm : 3671(w), 2956(m), 2919(m), 2851(m), 1595(w), 1521(w), 1458(w),
Ar
1
8
413(w), 1392(w), 1241(w), 1193(w), 1161(s), 1131(m), 1104(m), 1054(s), 1016(m), 921(m),
73(s), 841(s), 782(s), 746(m), 732(m), 680(w), 625(w), 593(s), 526(m), 468(w). Anal Calcd. for
C H O : C, 83.47; H, 7.00. Found: C, 83.66; H, 7.04.
70
70
6
2
.2.6.14. 4,8-Didecyl-2,3,6,7-tetrakis(4-((E)-3,5-di-tert-
butylstyryl)phenyl)benzo[1,2-b:4,5-b']difuran (21)
1
6

ACCEPTED MANUSCRIPT
Prepared from trans-2-(1,3-bis(tert-butyl)-5-phenyl)vinylboronic acid MIDA ester,
crystallized from chloroform/methanol, 0.480 g (99%) of yellow-green solid, mp=279.5-281.5 °C.
1
H NMR (CDCl , 400 MHz), δ ppm: 0.83 (t, J=7.0, 6H, 2CH ), 1.07-1.32 (m, 28H, 14CH ), 1.35 (s,
3
3
2
3
6H, 12CH ), 1.41 (s, 36H, 12CH ), 1.46-1.54 (m, 4H, 2CH ), 2.76-2.80 (m, 4H, 2CH ), 7.05-7.12
3 3 2 2
(
m, 4H, 4CH), 7.21-7.26 (m, 2H, 2CH ), 7.28-7.32 (m, 2H, 2CH ), 7.33-7.34 (m, 6H, 6CH ),
Ar Ar Ar
1
3
7
.40-7.44 (m, 10H, 10CH ), 7.51-7.53 (m, 8H, 8CH ), 7.65-7.70 (m, 4H, 4CH ). C NMR
Ar Ar Ar
(
CDCl , 100 MHz), δ ppm: 14.12 (2CH ), 22.71 (2CH ), 25.55 (2CH ), 29.37 (2CH ), 29.44
3 3 2 2 2
(
2CH ), 29.67 (2CH ), 29.73 (2CH ), 29.85 (2CH ), 30.94 (2CH ), 31.45 (12CH ), 31.51 (12CH ),
2 2 2 2 2 3 3
3
1.93 (2CH ), 34.85 (4C), 34.91 (4C), 116.03 (2C ), 118.54 (2C ), 120.88 (4CH ), 120.95
2 Ar Ar Ar
(
4CH ), 122.23 (4CH ), 125.97 (2C ), 126.37 (4CH ), 126.50 (4CH ), 126.89 (4CH ), 127.41
Ar Ar Ar Ar Ar Ar
(
2CH ), 127.70 (2CH ), 130.14 (2CH ), 130.25 (2CH ), 131.07 (4CH ), 133.95 (2C ), 136.42
Ar Ar Ar Ar Ar Ar
(
2C ), 136.54 (2C ), 136.99 (2C ), 137.28 (2C ), 149.79 (2C ), 149.83 (2C ), 150.41 (2C ),
Ar Ar Ar Ar Ar Ar Ar
-
1
1
1
51.06 (4C ), 151.09 (4C ). IR (ATR) ν cm : 2955(s), 2921(w), 1591(m), 1464(m), 1391(m),
Ar Ar max
361(m), 1249(m), 1096(m), 960(s), 898(w), 877(w), 858(s), 810(m), 703(s), 625(w), 514(w). Anal
Calcd. for C H O : C, 88.55; H, 9.45. Found: C, 88.18; H, 9.40.
1
18 150
2
2
.2.6.15. (((2E,2'E,2''E,2'''E)-((4,8-didecylbenzo[1,2-b:4,5-b']difuran-2,3,6,7-
tetrayl)tetrakis(benzene-4,1-diyl))tetrakis(prop-2-ene-3,1-diyl))tetrakis(oxy))-
tetrakis(triisopropylsilane) (22)
Prepared from trans-1-propenyl-3-triisopropylsilyloxyboronic acid MIDA ester, crystallized from
1
chloroform/methanol, 0.324 g (68%) of yellow solid, mp=144.5-146 °C. H NMR (CDCl , 700
3
MHz), δ ppm: 0.87 (t, J=14.0 Hz, 6H, 2CH ), 1.07-1.09 (m, 36H, 12CH ), 1.13-1.15 (m, 36H,
3
3
12CH ), 1.16-1.29 (m, 40H, 14CH 12CH), 1.43-1.47 (m, 4H, 2CH ), 2.68-2.70 (m, 4H, 2CH ),
3 2, 2 2
4
.41 (dd, J=4.8 Hz, J=1.8 Hz, 4H, 2CH ), 4.51 (dd, J=4.8 Hz, J=1.8 Hz, 4H, 2CH ), 6.24-6.30 (dt,
2
2
J=4.8 Hz, J=16.1 Hz, 2H, 2CH), 6.41-6.44 (dt, J=4.8 Hz, J=16.1 Hz, 2H, 2CH), 6.58 (d, J=16.1 Hz,
H, 2CH), 6.76 (d, J=16.1 Hz, 2H, 2CH), 7.23-7.28 (m, 4H, 4CH ), 7.38-7.45 (m, 8H, 8CH ),
2
Ar
Ar
1
7

ACCEPTED MANUSCRIPT
1
3
7
.50-7.52 (d, J=8.0 Hz, 4H, 4CH ). C NMR (CDCl , 125MHz), δ ppm: 12.07 (6CH-Si), 12.12
Ar 3
(
6CH-Si), 14.13 (2CH ), 18.02 (12CH ), 18.08 (12CH ), 22.73 (2CH ), 25.48 (2CH ), 29.34
3 3 3 2 2
(
2CH ), 29.42 (2CH ), 29.61 (2CH ), 29.69 (2CH ), 29.80 (2CH ), 30.88 (2CH ), 31.96 (2CH ),
2 2 2 2 2 2 2
6
3.89 (2CH ), 63.96 (2CH ), 115.97 (2C ), 118.35 (2C ), 125.89 (2C ), 126.29 (4CH ), 126.36
2 2 Ar Ar Ar Ar
(4CH ), 126.81 (4CH ), 128.55 (2CH), 128.82 (2CH), 129.65 (2CH), 129.72 (2CH), 130.00
Ar Ar
(
2C ), 130.89 (4CH ), 133.80 (2C ), 136.53 (2C ), 136.79 (2C ), 149.71 (2C ), 150.30 (2C ).
Ar
Ar
Ar
Ar
Ar
Ar
Ar
-1
IR (cm ): 3672(w), 2926(s), 2861(s), 1515(w), 1460(m), 1409(w), 1378(m), 1257(m), 1128(w),
1
063(s), 1012(s), 994(m), 962(m), 919(w), 881(s), 842(m), 779(m), 738(m), 681(s), 658(s), 573(w),
20(m), 458(w). Anal. Calcd. for C H O Si : C, 76.92; H, 10.00. Found: C, 77.26; H, 9.97.
5
1
02 158
6
4
3
.
Results and discussion
The aim of this work was the development and fluorescence characterization of new π-
conjugated BDF star-shaped systems containing symmetrically arranged aromatic, heteroaromatic
or vinyl-aryl substituents at positions 2,3,6,7 of the BDF core (Figure 1).
Figure 1. Star-shaped BDFs
To achieve this goal we planned to obtain the above BDF core, substituted with bromine at
para- position of all phenylene rings, and react it with appropriate boronic acids or MIDA esters in
the Suzuki coupling. In 1899 Japp and Meldrum reported the condensation of benzoin and
1
8

ACCEPTED MANUSCRIPT
hydroquinone in a presence of 73% sulfuric acid [44]. Their report was supplemented by
Dischendorfer who found that two benzodifuran isomers 1 and 2 were formed in these conditions
[45] (Scheme 1).
Scheme 1. Reaction of benzoin with hydroquinone in acidic conditions
Shukla and Rathore replaced sulfuric acid by zinc chloride in a solvent free reaction, and obtained
only 1 in high 80% yield [46]. Unfortunately in our hands the reaction gave an equimolar mixture of
1
and 2 in moderate yield (42%). Consequently, we decided to block positions 2 and 5 of
hydroquinone to enable the formation of only one desired isomer. To enhance solubility of the
preferred benzodifuran, a long-chained alkyl groups were introduced in these positions following
the protocol described by Bao and Yu [47] (Scheme 2).
Scheme 2. BDF synthesis by the zinc chloride mediated condensation of 3 with benzoin or 2-
chloro-1,2-diphenylethanone
1
9

ACCEPTED MANUSCRIPT
The zinc chloride mediated condensation of 3, produced exclusively the desired
benzodifuran 4 in 22% yield. Later much better results were obtained when 2-chloro-1,2-
diphenylethanone was used for the reaction instead of benzoin (49% yield). To the best of our
knowledge, this is the first report describing the reaction of α-haloketones and hydroquinones
leading to benzodifurans. The main drawback of the reaction of hydroquinone with benzoins is the
benzil formation, which is almost not observed when α-chloroketone is used. The traces of benzil
can be easily removed with perhydrol in the presence of sodium hydroxide to obtain pure 4 [48].
Thus, a similar procedure was used for the synthesis of tetrabromo-substituted BDF core
(Scheme 3).
Scheme 3. The synthesis of tetrabromo-substituted core for star-shaped 2,3,6,7-tetrasubstituted
BDFs
1,2-Bis(4-bromophenyl)-2-hydroxyethanone (5) was prepared by a simple cyanide
catalyzed benzoin condensation in good yield. The reaction with cyanuric chloride and DMF, using
De Luca and Giacomelli protocol [49], gave 1,2-bis(4-bromophenyl)-2-chloroethanone (6) in 78%
yield. Its reaction with 3, followed by oxidative purification, resulted in tetrabromo-BDF core 7,
44% yield. The Suzuki coupling reaction was performed using phenylboronic acid and
2
0

ACCEPTED MANUSCRIPT
phenylboronic acid MIDA ester. Bis(triphenylphosphine)palladium(II) dichloride - (Pd(PPh ) Cl )
3
2
2
and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) - (Pd(dppf)Cl ) in 1,4-dioxane
2
were used as a catalysts in a presence of 3M aqueous solution of tripotassium phosphate (Table 1).
Table 1. The Suzuki reaction of BDF 7 and phenylboronic acid/MIDA ester.
Catalyst
Time
[h]
8
Isolated
yield
Entry
Reactant
1
0% mol
[
%]
1
2
3
4
Phenylboronic acid
Phenylboronic acid
Pd(PPh ) Cl
2
68%
56%
75%
92%
3
2
Pd(dppf)Cl2
2
Phenylboronic MIDA ester Pd(PPh ) Cl
2
20
8
3
2
Phenylboronic MIDA ester Pd(dppf)Cl2
Although the reaction with phenylboronic acid proceeds in 2-8 h, instead of 20 h for MIDA
esters, but its yield is lower what is caused by slow hydrolysis of MIDA ester in basic conditions
and low concentration of the resulting acid which reacts immediately with 7, without side products.
Thus, for further BDF system elongation, 7 was reacted with an appropriate boronic acid MIDA
esters in the presence of Pd(dppf)Cl catalyst and tripotassium phosphate as a base in 1,4-
2
dioxane/water mixture (Table 2).
Table 2. The Suzuki reaction of BDF 7 and aryl, heteroaryl and vinyl boronic acid MIDA
esters.
Br
R
H C
3
N
O
C10H21
C10H21
B
O
O
R
O
O
O
Br
Br
R
R
O
Pd(dppf)Cl2, K PO
O
3
4,
C10H21
1,4-dioxane/water
T=80 °C , 18h
C10H21
-22
8
7
Br
R
Yield
%]
Yield
[%]
R
Product
R
Product
[
2
1

ACCEPTED MANUSCRIPT
8
92
16
17
37
69
9
99
1
0
1
2
93
48
37
18
19
20
42
99
49
1
1
1
3
40
21
22
99
68
1
1
4
5
61
49
The products were obtained in moderate to good yields, as amorphous yellow, orange or green
solids, well soluble in chloroform and dichloromethane, except 12, 16, and 19, not sufficiently
1
3
soluble for recording their C NMR spectra.
Table 3. Physical properties of BDFs 4-22.
-
6
3
Dichloromethane solution c=2.5×10 mol/dm
ε
c
c
b
Compound
λabs
nm)
λem
(nm)
HOMO
(eV)
LUMO
(eV)
Eg
(eV)
-1
-1
a
τ
F
M cm
φF
(
(ns)
2
3
29
56
70200
51200
4
387
0.89
1.01
-5.21
-1.64
3.58
2
2

ACCEPTED MANUSCRIPT
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
4
2
3
2
3
2
3
2
3
2
3
2
3
3
4
2
3
28
65
61
80
76
83
52
76
61
80
66
83
75
95
88
00
62
82
59
88
92
74
62
88
58
91
60
77
21
06
61
83
58900
57700
66700
75000
51900
64100
43100
57700
65800
76200
75000
77300
80100
73400
72100
70100
69100
76200
129000
79000
38500
71000
62500
60000
107500
74400
44300
67600
83100
92200
60300
70200
7
8
9
397
454
454
448
456
458
490
528
460
466
452
472
478
446
486
456
0.65
0.67
1.10
1.00
1.06
1.10
1.13
1.41
2.13
1.16
1.06
1.02
1.36
1.38
1.16
1.20
1.30
-5.49
-5.14
-4.95
-4.91
-5.04
-5.00
-5.68
-5.53
-5.28
-5.14
-5.19
-5.51
-5.33
-5.09
-4.94
-5.10
-2.02
-1.83
-1.65
-1.58
-1.71
-1.68
-2.53
-2.47
-1.99
-1.91
-1.83
-2.25
-2.14
-1.78
-1.99
-1.90
3.46
3.31
3.30
3.34
3.33
3.31
3.15
3.07
3.29
3.23
3.36
3.26
3.19
3.31
2.95
3.19
1
0.98
1
1
0
1
2
3
4
5
6
7
8
9
0
1
2
1
1
1
1
1
1
1
1
1
2
2
2
1
1
0.93
0.74
0.97
0.97
1
0.89
0.89
0.77
0.87
0.69
a
Quantum yield measured with a JASCO FP-8500 spectrometer against 9,10-diphenylanthracene in cyclohexane (θref = 0.95) at λ =
ex
b
3
66 nm. Absorbance of dye solution in dichloromethane between 0.0024 and 0.101 @ λabs = 366 nm. Fluorescence lifetime
determined by Time-Correlated Single-Photon-Counting (TCSPC) with PicoQuant (Germany) pulsed LED @ λex = 376 nm as light
a
c
source. The same solution as for . Calculated using B3LYP/Def2-SVP approximation.
The UV-Vis spectra of 8-22 showed two maxima in the regions 250-321 nm and 374-406 nm. For
compounds 13, 14, 16, 18, 19 the first band was more intense whereas for 8, 9, 10, 11, 12, 15, 17,
20, 21, 22, the second band was more intense. Among these products, the compound 16, containing
the 2-naphthyl group, exhibited the highest fluorescence intensity in dichloromethane solution,
taken as a combination of the molar extinction coefficient and fluorescence quantum yield (Table
3). It is noteworthy that the products 8, 10, 11, 12, 17 exhibit quantum yield of 100%, and 9, 13, 15,
16, over 90%. Lower, but still good quantum yield 69%, was achieved for 22, having the shortest π-
electronic system. The emission spectra of 8-22 in dichloromethane are shown in Figure 2.
2
3

ACCEPTED MANUSCRIPT
a)
b)
1
.8
.6
.4
.2
1
:
14
: 15
: 17
: 19
: 21
:
:
4
8
: 7
: 16
0
0
0
0
0.8
0.6
0.4
0.2
0
:
:
:
18
20
22
: 9
: 10
: 11
: 13
:
12
0
0
3
50
400
450
500
550
600
650
700
350
400
450
500
550
600
650
700
emission wavelength [nm]
emission wavelength [nm]
Figure 2. Emission spectra of a): 4, 7-13 and b): 14-22 in dichloromethane. Excitation wavelength
λex=366 nm. Concentration set to an absorbance value between 0.06 and 0.11 to avoid the inner
filter effect. The spectra are normalized to the maximal intensity.
An insight into the electronic structure of the investigated molecules was gained by the QM
calculations within the B3LYP/Def2-SVP approximation. The calculations were performed with
Gaussian 09 program package. Figure 3 presents the HOMO and LUMO orbitals of 8 which is
representative for the 2,6-substituted benzodifurans. Visualization of the HOMO and LUMO
molecular orbitals does not suggest any significant charge transfer during an electron excitation.
However the LUMO orbital reaching outside the molecule is observed.
2
4

ACCEPTED MANUSCRIPT
Figure 3. HOMO and LUMO orbitals of 8 calculated within the B3LYP/Def2-SVP approximation.
4. Conclusion
In summary, fifteen new aryl-, aryl-heteroaryl, and aryl-vinyl star-shaped BDFs were
prepared by a two step synthesis starting from of 1,2-bis(4-bromophenyl)-2-chloroethanone and
,5-didecylbenzene-1,4-diol by zinc chloride mediated condensation. It is the first report describing
2
reaction of α-haloketones and hydroquinones leading to benzodifurans. The next step involved the
Suzuki coupling reactions, leading to star-shaped BDFs in 37-99% yield. The desired products
exhibit the UV-Vis fluorescence with high to excellent quantum yields, 69-100%. Due to long-
chained alkyl groups at positions 4 and 8 of BDF core, these highly π-conjugated products are also
soluble in halogenated organic solvents.
Acknowledgments
Financial support from the Synthex Technologies Sp. z o.o. is acknowledged. Mariusz Bosiak
gratefully acknowledge Prof. Marek Zaidlewicz and Dr Marzanna Kurzawa.
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2
5

ACCEPTED MANUSCRIPT
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Synthesis of benzodifuran star-shaped luminophores
A new reaction of α-haloketones with hydroquinones leading to benzodifurans
The Suzuki coupling of MIDA esters
Benzodifurans of fluorescence quantum yield 69-100%
Highly π-conjugated systems soluble in organic solvents