Bis(porphyrin)-3,4:9,10-perylenetetracarboxydiimide triads as new building blocks for the synthesis of aromatic polyethers

Article abstract of DOI:10.1134/S0012500816010031

It was shown that aromatic polyethers (APs) containing in the main chain bis(porphyrin) perylenediimide triads as new building blocks can be obtained. Thermal properties of the prepared APs showing high glass transition temperature were studied. Negative photoresists based on the final unsaturated polymer and anthrylsulfonium salt were designed.

Full text of DOI:10.1134/S0012500816010031

ISSN 0012ꢀ5008, Doklady Chemistry, 2016, Vol. 466, Part 1, pp. 3–7. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.Ya. Vainer, K.M. Dyumaev, A.M. Kovalenko, R.M. Dragunskaya, T.D. Bel’skii, I.Ya. Khait, 2016, published in Doklady Akademii Nauk, 2016,
Vol. 466, No. 2, pp. 169–173.
CHEMISTRY
Bis(porphyrin)ꢀ3,4:9,10ꢀperylenetetracarboxydiimide Triads
as New Building Blocks for the Synthesis
of Aromatic Polyethers
A. Ya. Vainer, Corresponding Member of the RAS K. M. Dyumaev,
A. M. Kovalenko, R. M. Dragunskaya, T. D. Bel’skii, and I. Ya. Khait
Received July 21, 2015
Abstract—It was shown that aromatic polyethers (APs) containing in the main chain bis(porphyrin)
perylenediimide triads as new building blocks can be obtained. Thermal properties of the prepared APs showꢀ
ing high glass transition temperature were studied. Negative photoresists based on the final unsaturated polyꢀ
mer and anthrylsulfonium salt were designed.
DOI: 10.1134/S0012500816010031
Chemical modification of aromatic polyethers APs whose macromolecules contain covalently
(
APs) allows considerable extension of functional posꢀ bound bis(porphyrin)perylenediimide triads are not
sibilities of these polymers, in particular, such transꢀ described in the literature.
formations increase application efficiency of APs in
In this paper, we proposed for the first time a
different areas of aerospace industry and microelecꢀ
tronics [1, 2]. Thus, we showed recently [2] that unsatꢀ
urated APs with side adamantane fragments can find
practical application as a base of negative photoresists
promising in manufacture of semiconductor devices.
However, known APs exhibit relatively low heatꢀdisꢀ
tortion temperature, which can result under plasmoꢀ
chemical etching conditions in thermal distortion of
image obtained by film exposition.
strategy for the synthesis of APs containing the
above triads in the main chains. A series of consecꢀ
utive chemical transformations of APs was carried
out to prepare unsaturated polymers with side tetꢀ
rafluorostyryl groups. Moreover, we studied thermal
and photochemical transformations of the obtained
APs and assessed lithographic parameters of negaꢀ
tive photoresists developed on the basis of desired
AP derivatives in the course of formation of topoꢀ
logical structures.
Heatꢀdistortion temperature of condensation
polymers usually increases on introduction of rigid
aromatic fragments into the main chain. Therefore
We synthesized 5ꢀ(pentafluorophenyl)ꢀ10,20ꢀ
we turned our attention to such promising in our bis(3',5'ꢀdimethoxyphenyl)ꢀ15ꢀ[4''ꢀ(4''',4''',5''',5'''ꢀ
opinion structures as porphyrins [3] and perylenediꢀ tetramethylꢀ1''',3''',2'''ꢀdioxaborolanꢀ2'''ꢀyl)pheꢀ
imides [4] showing unique chemical, photochemiꢀ nyl]porphyrin (I) and N,N'ꢀbis(3',5'ꢀdimethoxybenꢀ
cal, and thermal stability. In recent years, a certain zyl)ꢀ1,7ꢀdibromoperyleneꢀ3,4:9,10ꢀbis(dicarboximꢀ
interest has been attracted to symmetrical covalentꢀ ide) (1,7ꢀII), which were used for the synthesis of new
bonded triads of porphyrins with perylene structures bis(porphyrin)perylenediimide triads. The latter were
as core units. These triads are useful as supramolecuꢀ further employed as building blocks for the modificaꢀ
lar systems for the development of different optoelecꢀ tion of AP main chains.
tronic devices [5, 6]. It is reasonable to suppose that
Porphyrin I was obtained by the Suzuki–Miyaura
crossꢀcoupling reaction [7] under an argon atmoꢀ
sphere via condensation of 5ꢀ(pentafluorophenyl)ꢀ
building blocks based on such porphyrin systems
when introduced into the main chains of APs will
increase considerably the heatꢀdistortion temperaꢀ
ture of these polymers. Let us note that, until now,
1
0,20ꢀbis(3',5'ꢀdimethoxyphenyl)ꢀ15ꢀ(4''ꢀbromopheꢀ
nyl)porphyrin (III) with bis(pinacolato)diboron (Aldꢀ
rich) (Scheme 1) in dimethyl sulfoxide (DMSO) using
dichloro[1,1'ꢀbis(diphenylphosphino)ferrocene]palꢀ
AllꢀRussian Research Institute of Medicinal and Aromatic
Plants, ul. Grina, 7ꢀ1, Moscow, 117216 Russia
ladium ([(dppf)Fe]PdCl ) (Strem Chemical Co.,
2
eꢀmail: nvbarannik@mail.ru
United States).
3

4
VAINER et al.
Me C CMe
2
2
O
O
Br
B
MeO
MeO
OMe
MeO
MeO
OMe
OMe
NH
N
NH
N
N
N
HN
HN
OMe
F
F
F
F
F
F
F
F
F
F
I
III
Scheme 1. Reagents and reaction conditions: KOAc, DMSO, bis(pinacolato)diboron, [(dppf)Fe]PdCl , 80
°
C, 4 h, 58%.
2
Porphyrin III, in its turn, was prepared by proceꢀ Next, under an argon atmosphere, the resultant at the
dure [8] through condensation of pyrrole with 2,3,4,5ꢀ previous stage mixture of brominated derivatives of
pentafluorobenzaldehyde, 3,5ꢀdimethoxybenzaldehyde, perylenetetracaboxylic dianhydride (the main bromiꢀ
and 4ꢀbromobenzaldehyde (products from Aldrich).
Diimide 1,7ꢀII was obtained by procedure [9]. Iniꢀ
tial peryleneꢀ3,4:9,10ꢀtetracaboxylic dianhydride (IV
nation product is 1,7ꢀdibromoꢀIV) was imidated by
reacting with 3,5ꢀdimethoxybenzylamine (Aldrich).
Compound 1,7ꢀII was isolated from reaction mixture
)
(
Aldrich) was subjected to bromination in the presꢀ by procedure [10] through triple recrystallization from
ence of catalytic amounts of iodine [9] (Scheme 2). a CH Cl –CH OH (1 : 1, v/v) mixture.
2
2
3
OMe
OMe
O
O
O
O
N
O
X
a, b
Br
X
Br
O
O
O
O
N
O
IV
MeO
OMe
1
,7ꢀII
X =H (IV), Br (1,7ꢀIV
Scheme 2. Reagents and reaction conditions
dimethoxybenzylamine, 140 С, 4 h, 25%.
)
:
(
a
) Br , I , 98% H SO , 85
°
C, 11 h, 87%; (b) imidazole, 3,5ꢀ
2
2
2
4
°
DOKLADY CHEMISTRY Vol. 466
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BIS(PORPHYRIN)ꢀ3,4:9,10ꢀPERYLENETETRACARBOXYDIIMIDE TRIADS
5
And finally, new bis(porphyrin)perylenediimide
triads
condensation reaction from porphyrin
brominated perylene 1,7ꢀII in a mixture of dimeꢀ MALDI–TOF mass spectrometry, H, F, a n d C NMR
thylacetamide (DMA) and toluene (1 : 2, v/v) as well as by IR spectroscopy, and confirmed by analytical
under an argon atmosphere by procedure [11] HPLC and elemental analysis data. The table displays
Newly synthesized compounds
I
–
III and
V
were
V
were obtained by the Suzuki–Miyaura purified by preparative highꢀperformance liquid chromaꢀ
and tography (HPLC). Their structure was established by
I
1
19
13
(
Scheme 3).
molecular weights of the obtained compounds.
F
F
F
F
F
MeO
MeO
OMe
NH
N
N
HN
OMe
O
OMe
N
OMe
O
O
OMe
I + 1,7ꢀII + I
N
MeO
O
MeO
MeO
OMe
NH
N
N
HN
OMe
F
F
F
F
F
V
Scheme 3. Reagents and reaction conditions: Pd(PPh ) , Cs CO3, DMA, toluene, 85°С, 3 h, 76%.
3
4
2
Initial polymers containing fragments of triads
the main chains were prepared by nucleophilic substiꢀ precipitation into methanol, the deposited polymer
tution at condensation of compound and was separated by filtration, washed many times with
,7ꢀdibromoꢀ9,9'ꢀbis(4'ꢀhydroxyphenyl)fluorene. The methanol, next with ether and dried in a vacuum at
latter was obtained by procedure [12]. This condensaꢀ 70 C. The polymer is characterized by good solubility
tion was carried out by previously developed by us proꢀ in amide solvents, acetonitrile, and DMSO. The conꢀ
cedure [8] in DMA using CsF as a catalyst. The reacꢀ densation of triad and bromoꢀcontaining bisphenol
tion was conducted at 22 C under an argon atmoꢀ can be represented by Scheme 4. Then, we conducted
V in sphere for 3 h. The prepared AP VI was isolated by
V
2
°
V
°
DOKLADY CHEMISTRY Vol. 466
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2016

6
VAINER et al.
Molecular weights of prepared compounds
methoxymethoxyphenylboronic acid VII prepared by
procedure [13]. The reaction was conducted by proceꢀ
dure [14] using complex of tris(dibenzylideneaceꢀ
tone)dipalladium [Pd (dba) ] (Strem Chemical Co.,
Molecular weight, g/mol
Comꢀ
pound
Molecular
formula
2
3
found*
calculated
United States) with 1,3ꢀbis(2',6'ꢀdiisopropylpheꢀ
nyl)imidazolyl chloride (IPr HCl) as a catalyst [14].
I
С H BF N O
4 6
950.7786
848.5183
903.7148
2336.3129
950.7789
848.5181
903.7156
2336.3133
⋅
54
44
5
According to elemental analysis data, the condensaꢀ
tion proceeds in virtually quantitative yield.
1,7ꢀII C H Br N O
40 24 2 2 8
III
V
C H BrF N O
48 32 5 4 4
Polymer VIII with side methoxy groups was subꢀ
jected to demethylation by procedure [14] to give pheꢀ
C138H N F O
92
10 10 16
nolꢀcontaining AP IX. Final polymer
X was obtained
*
According to MALDI–TOF mass spectrometry.
by nucleophilic substitution of phenolic hydroxyls
with pentafluorostyrene. Let us note that, for the sake
a series of consecutive chemical transformations to of simplicity, Scheme 4 shows only transformations
introduce side tetrafluorostyryl groups into AP macroꢀ with participation of fluorene fragments of AP; reacꢀ
molecules. Scheme 4 displays the performed transforꢀ tions b and c in the case of functional groups attached
mations of initial AP VI. Brominated fluorene fragꢀ to porphyrin and perylenediimide structures in the
ments of the main chains of AP were condensed by the chains of these macromolecules proceed in similar
Suzuki–Miyaura reaction with 3,4ꢀdimethoxyꢀ2ꢀ manner.
F
TRD
F
OH
Br
OH
Br
F
F
2
F
F
F
F
F
F
F
F
O
F
O
F
F
TRD
TRD
Br
Br
n
a, b, c
F
F
F
O
F
O
F
F
TRD
TRD
Ar
Ar
n
F
F
OR
F
R'O
OR
c
Ar =
R = R'=
F
Scheme 4. TRD =
conditions: ( VII, [Pd (dba) ]
pentafluorostyrene, СаН , СsF, DMAA, 80
V
=
bis(pentafluorophenyl) (
(IPr HCl), dioxane, 80
C, 18 h, 100%.
а
) R = –Me; R' = –OCH Me, (
b
) R = R' = –H. Reagents and reaction
2
а)
⋅
·
°
С, 48 h, 100%; (
b)
VIII, BBr , CH Cl , 22 C, 10 h, 100%; ( IX,
°
с)
2
3
3
2
2
°
2
DOKLADY CHEMISTRY Vol. 466
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BIS(PORPHYRIN)ꢀ3,4:9,10ꢀPERYLENETETRACARBOXYDIIMIDE TRIADS
7
The structure of APs prepared in this work was conꢀ transition temperature of the prepared APs. For examꢀ
1
19
13
firmed by IR data and H, F, a n d C NMR spectra. ple, the latter for phenolꢀcontaining AP IX is 354
Thus, the IR spectrum of initial AP VI
Such a high lithographic parameters of resists based on
.39 dL/g, 0.5% solution in DMA, 25 C) exhibits
absorption bands typical for fiveꢀmembered imide
°C.
(
η
=
red
the prepared APs exceed considerably those for
recently proposed lightꢀsensitive system [15].
0
°
–
1
rings: 1707, 1668, 1356, and 730 cm . Let us note the
Thus, we showed, for the first time, the possibility
–1
presence of absorption band at 3320 cm (NH in pyrꢀ to prepare APs containing bis(porphyrin)perylenediꢀ
role fragments) in the IR spectra of all studied polyꢀ imide triads in the main chain as building blocks. We
mers.
V
developed a simple and convenient method for the
synthesis of these polymers and performed a series of
sequential chemical transformations of APs to proꢀ
duce an unsaturated polymer with tetrafluorostyryl
side groups. Thermal properties of the prepared APs
with high glass transition temperature were studied.
1
The H NMR spectrum of polymer IX displays
proton signals of phenolic groups at 10.24 ppm, which
is absent in AP X. On the contrary, the latter spectrum
shows new signals due to different protons of fluoꢀ
rostyrene fragments. The signals at 5.74 ppm
Negative photoresists based on AP X and anthrylsulfoꢀ
(
CH =CH–) and 6.14 ppm (CH =CH–) have anaꢀ
2
2
nium salt were developed. The designed photoresists
were shown to have high lithographic parameters.
These resists can be promising in manufacture of
semiconducting devices.
lytical value. The spectra of polymers VI and VIII disꢀ
play a singlet signal at 3.89 ppm related to the protons
of methoxy groups. This signal disappears in the specꢀ
trum of polymer IX owing to demethylation.
Analytical procedures were reported elsewhere [8, 14].
13
The C NMR spectra of the prepared polymers
exhibit signals of carbon atoms of imide carbonyls at
1
63.05 and 162.9 ppm, as well as signals of carbon
REFERENCES
atoms in the perylene scaffolds at 134.9, 129.4, 127.5,
1
. Wan, Y., Zhang, Y., Shi, Z., et al., Polymer, 2012,
vol. 53, no. 4, pp. 967–975.
13
1
23.5, and 123.2 ppm. The C NMR spectrum of
modified AP displays new signals corresponding to
the carbon atoms in the side vinyl groups at 123.7 ppm
CH =CH–) and 121.8 ppm (CH =CH–). The 19
X
2. Vainer, A.Ya., Dyumaev, K.M., Mareeva, S.A., et al.,
Dokl. Phys. Chem., 2014, vol. 454, part 2, pp. 25–28.
(
F
3. Li, M., Xu, H. Yang, Y., et al., Chem. Lett., 2014, vol. 43,
2
2
no. 11, pp. 1764–1766.
NMR spectrum of final polymer
X shows new signals
4
5
6
7
8
9
. Huang, C., Barlow, S., and Marder, S.R., Org. Chem.
,
at –144.1 and –155.6 ppm from the fluorine atoms in
the side 2,3,5,6ꢀtetrafluorostyrene groups.
The resulting APs with bis(porphyrin)perylenediꢀ
imide triads in the main chains exhibit high thermal
stability. For example, the temperature of 5% weight
loss for phenolꢀcontaining polymer IX on heating
2011, vol. 76, no. 8, pp. 2386–2407.
. You, C.C. and Würthner, F., Org. Lett., 2004, vol. 6,
no. 14, pp. 2401–2404.
. Ghirotti, M., Chiorboli, C., You, C.C., et al., J. Phys.
Chem. A, 2008, vol. 112, no. 15, pp. 3376–3385.
. Ishiyama, T., Murata, M., and Miyaura, N., Org.
Chem., 1995, vol. 60, no. 23, pp. 7508–7510.
. Vainer, A.Ya., Dyumaev, K.M., Dragunskaya, R.M.,
et al., Dokl. Chem., 2015, vol. 461, part 1, pp. 70–74.
. Würthner, F., Stepanenko, V., Chen, Z., et al., Org.
Chem., 2004, vol. 69, no. 23, pp. 7933–7939.
under an argon atmosphere is 579
tion of side tetrafluorostyrene groups in the main
chain of AP slightly decreases this parameter to 566
In this work, we developed new negative photoreꢀ
°С. The introducꢀ
°С
.
sists based on unsaturated polymer
cyanobenzyl)methylsulfonium
X
and anthryl(4'ꢀ
1
0. Shao, C., Grüne, M., Stolte, M., and Würthner, F.,
trifluoromethaneꢀ
Chem. Europ. J., 2012, vol. 18, no. 43, pp. 13665–
sulfonate. The latter was obtained by procedure [14].
The content of anthryllsulfonium salt in AP was 7.5 wt %.
These resists exhibit high light sensitivity: optimal
13677.
11. Aratani, N., Cho, H.S., Ahn, J.K., et al., J. Am. Chem.
Soc., 2003, vol. 125, no. 32, pp. 9668–9681.
2
exposure dose was equal to 127 mJ/cm on irradiation
1
2. Wang, P.ꢀH., Ho, M.S., Yang, S.H., et al., J. Polym.
Sci.: Polym. Chem. Ed, 2010, vol. 48, no. 3, pp. 516–
by light of 365 nm wavelength.
5
24.
13. McElroy, W.T. and DeShong, P., Tetrahedron, 2006,
vol. 62, no. 29, pp. 6945–6954.
The studied resists have high resolution (topologiꢀ
cal structures with minimal size of elements of 0.6
μ
m
were formed in a 1.0ꢀ m polymer film based on AP X)
μ
1
4. Vainer, A.Ya., Dyumaev, K.M., Kovalenko, A.M.,
and plasma resistance adequate to contemporary
lithography. The linear size alteration of topological
elements during plasmaꢀchemical etching of these
et al., Dokl. Chem., 2014, vol. 458, part 2, pp. 189–193.
15. Inoue, Y., Higashihara, T., and Ueda, M., J. Photoꢀ
polym. Sci. Technol., 2013, vol. 26, no. 3, pp. 351–356.
resists based on AP
X
is not larger than 0.04 m. The
μ
high reproducibility of linear size of micro images is
explained, in our opinion, by the rather high glass
Translated by I. Kudryavtsev
DOKLADY CHEMISTRY Vol. 466
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2016