V.D. Ghase et al.
Polymer 209 (2020) 122947
of substituted dibenzofluorene monomer instead of fluorene. Owing to
the broad steric group substitution, the crystallinity of synthesized
polymers decreases which can make them suitable for display applica-
tions. This research investigates the thermal, photophysical, and elec-
trochemical properties of these polymers.
60.42; 118.201; 128.25; 124.58; 126.05; 128.44; 129.81; 129.91;
133.62; 139.13; 145.63; MS (m/z) 368; Anal. Calcd for C27H24: C,
93.10%; H, 6.89% Found: C, 92.64%; H, 7.36%.
2.3.3. Synthesis of 5,8- dibromo-13,13-dipropyl-13H-dibenzo[a,i]fluorene
M1)
A mixture of 13,13-dipropyl-13H-dibenzo [a, i]fluorene (1 g, 0.003
(
2
. Experimental section
mmol) and NBS (1,3 g, 0.007 mmol) in DMF was stirred at room tem-
perature for 24 h and then extracted with chloroform. Separated organic
2
.1. Materials and methods
2 4
layer, washed with brine, and dried over anhydrous Na SO . After
A.R. grade chemicals required were purchased from SD fine and
evaporation of the solvent, crude product obtained was purified using
column chromatography (eluent: petroleum ether: chloroform 9:1 v/v)
to afford a light brown solid (Fig. 1).
Sigma Aldrich. Nitrogen atmosphere was employed while conducting all
synthetic processes. Only THF was distilled using sodiumbenzopheno-
neketyl. The diphenol monomers 4,4’-(anthracene-9,10-diyl)diphenol
ꢀ 1
IR (KBrcm ): 3047 (s), 2952 (s), 2926 (w), 1583 (s), 1459 (m), 908
◦
1
(
DPA), 4,4’-(2- methylanthracene-9,10-diyl)diphenol (MDPA), 4,4’-(2-
(s), 816 (m), 754 (s), M.P.: 215–218 C, H NMR (300 MHz, CDCl
(t, 6H, –CH ), 0.46 (m, 4H, –CH CH ), 2.67 (m, 4H, –CH CH
7.25–8.56 (10H, Ar–H), C NMR (75 MHz, CDCl ): 14.2, 17.1, 42.4,
60.4, 119.3, 127.7, 124.8, 128.1, 129.2, 129.5, 129.9, 134.9, 139.2,
45.8, MS (m/z): 508; Anal. Calcd for C27 24Br : C, 63.77%; H, 4.72%
Found: C, 63.64%; H, 4.55%.
3
): 0.24
ethylanthracene-9,10-diyl)diphenol (EDPA) and 4,4’-(2-(tertbutyl)
anthracene-9,10-diyl)diphenol (TBDPA) were prepared and character-
ized previously [25–29].
3
2
3
2
2
CH ),
3
1
3
3
1
H
2
2
.2. Instrumentation-
The elemental analysis of M1, M2 and polymers (P1–P4) was per-
2.3.4. Synthesis of 9,10-di(p-hydroxyphenyl)anthracene (M2)
formed on Euro Vector EA 3000 instrument using microanalytical
This monomer was synthesized and characterized by the method
reported in our previous investigation [25–30]. By using various qui-
nones five different acene monomers were (M2a, M2b, M2c and M2d)
obtained. Detail scheme for the synthesis and its characterization
1
13
technique. Bruker AMX-300 NMR spectrometer was used for H and
analysis of all synthesized compounds. GC-MS Shimadzu GCMS/QP
010 was used to determine molecular weights of the compounds. Thin
C
2
Layer Chromatography analyses were performed to confirm the purity of
compound on plates coated with silica gel G (Merck). The X-Ray dif-
fractograms were recorded on Shimadzu XRD-7000. Shimadzu UV-2100
spectrophotometer were used to record UV spectra. PerkinElmer In-
struments LS55 Luminescence Spectrometer of wavelength range
included in supporting file. (Figure S
1 2
and Figure S supporting
information).
2.4. General polymerization
2
00–800 nm were use to study photoluminescence behaviour of com-
A mixture of M1 [5,8- dibromo-13,13-dipropyl-13H-dibenzo [a,i]
fluorene]and M2 [4,4’-(2-R-anthracene-9,10-diyl)diphenol monomer
(R = H (DPA), methyl (MDPA), ethyl (EDPA) or tert-butyl (TBDPA)];
0.001 mol) were taken in a three necked round bottom flask and added
potassium carbonate as a base. Then toluene and dioxane in 1:2 were
added in the flask and refluxed for 12 h. Excess M1 was added for end
capping of hydroxyl groups after polymerization. Water was added to
the reaction mixture. The solvent was evaporated to precipitate the
polymer and was further extracted using dichloromethane [20,23]. The
brown coloured polymers with a yield of 75–79% were obtained.
Changing monomers M2a, M2b, M2c, and M2d, polymers P1–P4
were prepared (Fig. 2).
pounds. PerkinElmer series 200 GPC was used for molecular weight
determination. Morphology was studied on Hitachi S-4800 field emis-
sion scanning electron microscope (Japan) SEM instrument.
2
2
.3. Synthesis of monomers
.3.1. Synthesis of dibenzofluorene (DBF)
Bis-(naphthalyl-1-yl)methanol (3.66 mg, 10 mmol) was heated in
◦
H
3
PO
4
(85% water; 30 ml) in an oil bath for 3 h at 180 C. Chloroform
and water were added after the reaction was completed, and organic
layers separated and washed by saturated Na CO , saturated NaCl, and
dried over Na SO . Light yellow white solid was obtained after purifi-
2
3
2
4
cation with chromatographic columns (silica gel, PET: CHCl
The product yield was 85%.
3
, 10:2 v/v).
2.4.1. NMR and FTIR signals, elemental analysis, molecular weight of
polymers [Poly(DBF)s]
ꢀ 1
1
IR (KBr cm ): 3131(S); 1589(S); H NMR (300 MHz, CDCl
3
) 4.41 (S,
): 34.41;
24.48; 125.40; 125.53; 125.86; 126.92; 128.56; 130.75; 132.21;
Poly[4,4’-(anthracene-9,10- diyl)diphenyloxy-co-13,13-dipropyl-
1
3
1
2
1
1
5
H); 6.99–7.94 (m, 12H, Ar-ring); C NMR (75 MHz, CDCl
3
13H-dibenzo[a,i]fluorenyl-5,8-diyl] [P1]: H NMR (300 MHz, CDCl
3
,
δ, ppm): 0.34 (t, 6H, –CH
–CH CH ), 7.55–8.31 (m, 26H, Ar–H), C NMR (75 MHz, CDCl
14.19 (CH ), 17.06 (-CH CH ), 46.93 (-CH CH CH ), 60.40 (C(Pr)2),
3
), 2.66 (m, 4H, –CH
2
CH
2
CH
3
), 0.50 (m, 4H,
13
32.70; 137.49; MS (m/z) 266; Anal. Calcd for C21
H
16: C, 94.03%; H,
2
3
3
, δ, ppm):
.97% Found: C, 93.87%; H, 6.13%.
3
2
3
2
2
3
ꢀ
1
1
18.68–145.78 (C arom.)- IR (KBr,cm ): 3055 (s) [H–C arom.], 1607 (s)
–
–
2
.3.2. 13,13-Dipropyl-13H-dibenzo[a,i]fluorene
[C
C], 2930 (s) [H–C aliph.], 1504 (b), [C–C arom.], 1042 (s) [C–O–C];
23: C, 91.51%;
In a flask, dibenzofluorene (1 g, 0.004 mmol), 50% aqueous NaOH
Mw/Mn: (25711/15985) = 1.60; Anal. Calcd for C1219
966
H O
and a catalytic quantity of tertiary butyl ammonium iodide (TBAI) (0.14
g, 0.004 mmol) were added under nitrogen atmosphere. 1-Bromo pro-
pane (3.5 ml, 0.02 mmol) was added slowly to the flask and then heated
for 5 h at 100–110 ◦C. The reaction mixture was cooled and extracted
chloroform then organic layer was washed twice with water and dried
H, 6.19%; O, 2.30%. Found: C, 91.48%; H, 6.12%; O, 2.40%.
Poly[4,4’-(2-methylanthracene-9,10-diyl)diphenyloxy-co-
1
13,13-dipropyl 13H-dibenzo[a,i] fluorenyl-5,8-diyl] [P2]: H NMR
(300 MHz, CDCl
3
, δ, ppm): 0.20 (t, 6H, CH
CH CH ), 2.94 (s, 3H, Ar-CH
Ar–H); C NMR (75 MHz, CDCl , δ, ppm): 14.29 (CH
(CH CH ), 42.98 (CH CH CH ), 58.34 (C(Pr) ), 24.75(Ar-CH
119.61–155.78 (C arom.), IR (KBr, cm ): 3059 (s) [H–C arom.], 1602
2
CH
3
) 0.41 (m, 2H, CH
) 6.93–8.35 (m, 25H,
CH ), 17.56
),
2 3
CH )
2.55 (m, 2H, CH
2
2
3
3
1
3
over anhydrous Na
2 4
SO . Product purification was done by chromatog-
3
2
3
raphy of the silica gel column using PET ether as a solvent to provide
light yellow solid with a yield of 80% [23,24].
2
3
2
2
3
2
3
ꢀ 1
ꢀ 1
◦
1
–
(s) [C
–
IR (KBr cm ): 2949(S); 2926.75 (S); 1590(S);; M.P-190-191 C; H
NMR (300 MHz, CDCl ) 0.28 (t, 6H,-CH ); 0.44 (m, 2H,-CH ); 2.72 (m,
H, –CH ); 8.33 (d, 2H); 7.9 1 (m, 2H); 7.55 (m, 2H); 7.43 (m, 2H); 7.24
d, 2H); 7.68 (d, 2H); C NMR (75 MHz, CDCl
C], 2932 (s) [H–C aliph.], 1508 (b) [C–C], 1034 (s) [C–O–C];
24: C,
3
3
2
Mw/Mn: (27313/16992) = 1.60; Anal. Calcd for C1296
1056
H O
2
2
91.52%; H, 6.21%; O, 2.27%. Found: C, 91.60%; H, 6.17%; O 2.23%.
1
3
(
3
) 14.28; 17.11; 42.30;
Poly[4,4’-(2-ethylanthracene-9,10-diyl)diphenyloxy-co-13,13-
2