Synthesis and optical properties of new 5′-aryl-substituted 2,5-bis(3-decyl-2,2′-bithiophen-5-yl)-1,3,4-oxadiazoles

Article abstract of DOI:10.3762/bjoc.13.34

New photoluminescent donor-acceptor-donor (DAD) molecules, namely 5′-aryl-substituted 2,5-bis(3-decyl-2,2′-bithiophen-5-yl)-1,3,4-oxadiazoles were prepared by palladium-catalyzed coupling from readily available compounds such as ethyl 3-decyl-2,2′-bithiop

Full text of DOI:10.3762/bjoc.13.34

Synthesis and optical properties of new 5'-aryl-substituted
2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles
Anastasia S. Kostyuchenko1,2, Tatyana Yu. Zheleznova1, Anton J. Stasyuk3,
Aleksandra Kurowska4, Wojciech Domagala4, Adam Pron*5 and Alexander S. Fisyuk*1,6
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2017, 13, 313–322.
1Laboratory of New Organic Materials, Omsk State Technical
University, Mira Ave, 11, 644050 Omsk, Russian Federation,
2Department of Organic Chemistry, Faculty of Science, RUDN
University, 6 Miklukho-Maklaya st., 117198 Moscow, Russian
Federation, 3Department of Chemistry and RECETOX, Masaryk
University, Kamenice 5, 625 00 Brno, Czech Republic, 4Department
of Physical Chemistry and Technology of Polymers, Silesian
University of Technology, Marcina Strzody 9, 44-100 Gliwice, Poland,
5Faculty of Chemistry , Warsaw University of Technology,
Noakowskiego 3, 00-664 Warszawa, Poland and 6Department of
Organic Chemistry, Omsk F.M. Dostoevsky State University, 55a Mira
pr., 644077 Omsk, Russian Federation
doi:10.3762/bjoc.13.34
Received: 09 October 2016
Accepted: 03 February 2017
Published: 17 February 2017
Associate Editor: P. J. Skabara
© 2017 Kostyuchenko et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Email:
Adam Pron* - apron@ch.pw.edu.pl; Alexander S. Fisyuk* -
fisyuk@chemomsu.ru
* Corresponding author
Keywords:
bithiophene; donor–acceptor; luminescence; 1,3,4-oxadiazole;
palladium-catalyzed coupling
Abstract
New photoluminescent donor–acceptor–donor (DAD) molecules, namely 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-
1,3,4-oxadiazoles were prepared by palladium-catalyzed coupling from readily available compounds such as ethyl 3-decyl-2,2'-
bithiophene-5-carboxylate and aryl halides. The obtained compounds feature increasing bathochromic shifts in their emission spec-
tra with increasing aryl-substituent size yielding blue to bluish-green emissions. At the same time, their absorption spectra are
almost independent from the identity of the terminal substituent with λmax values ranging from 395 to 405 nm. The observed trends
are perfectly predicted by quantum chemical DFT/TDDFT calculations carried out for these new molecules.
Introduction
π-Conjugated donor–acceptor (D-A) compounds are of signifi- trochemical properties [1-5]. Molecules in which a central elec-
cant scientific interest because they frequently combine solu- tron-accepting ring separates two bithiophene units are of par-
tion processability with unique electronic, luminescent and elec- ticular interest [6-15]. The continuing progress in this field calls
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Beilstein J. Org. Chem. 2017, 13, 313–322.
for elaboration of new synthetic procedures affording tailor- cyclic ring, the position of the solubilizing alkyl substituent and
made molecules with tunable physical properties. In this the molecule topology (linear vs three-arms star) [16,19,21,23].
respect, we have recently developed an efficient and flexible ap- In particular, the synthesized molecules turned out efficient
proach to the synthesis of π-conjugated donor–acceptor com- electroluminophores in organic light emitting diodes of
pounds [16,17]. The proposed synthetic pathway enables the “guest–host”-type [18,22,23].
preparation of linear D–A–D compounds with one or two 1,3,4-
oxadiazole [16-19], 1,3,4-thiadiazole [16,18-22] or 1,2,4-tri- In one of our previous papers [25] we proposed an original
azole [16,18] central rings symmetrically disubstituted with method for the preparation of ester derivatives of alkylbithio-
alkylbithiophene 1, 2 as well as star-shaped molecules with phenes 7, some of which were then used as precursors of 1–3
D–A arms 3 (Figure 1) [23].
(see Scheme 1)
We have also shown that these molecules, if the α-position in The ethyl esters of 2,2'-bithiophenes 7 having no (7a), an alkyl
the terminal polymer ring is not blocked, can electrochemically (7b), or a thienyl (7c) substituent in the C-5' position can be
polymerize yielding either linear polymers [17,19,20,24] or easily obtained by this method. On the other hand, the substitu-
polymeric networks [23]. It has been demonstrated that the tion of the thiophene ring with phenyl or fused aromatic rings is
optical and electrochemical properties of these new, solution- much more challenging and requires the elaboration of a new
processable and conjugated compounds can be modified in a synthetic procedure. In this communication we present a
controllable way by the nature of the electron-accepting hetero- detailed study of cross-coupling reactions between еthyl
Figure 1: D–A compounds 1–3.
Scheme 1: Synthesis of 3-decyl-2,2'-bithiophene-5-carboxylic acid ethyl esters 7a–c.
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Beilstein J. Org. Chem. 2017, 13, 313–322.
3-decyl-2,2'-bithiophene-5-carboxylate and different aryl the yield of the phenyl-substituted product 7d remained low
halides. The resulting esters are subsequently used as substrates (18%), even when the reaction was performed for 55 h after
in the preparation of new D–A–D compounds with an oxadia- which time all 7a had been consumed as judged by TLC. The
zole central ring symmetrically functionalized with bithiophene other products 7e–g could be isolated in 42–60% yield after
end-capped with various aryl groups. Our preliminary studies purification by column chromatography (Table 1).
show that these compounds can be used as electroluminophores
in LEDs, which show superior performance as compared to the With the building blocks 7b–g at hand, we next turned towards
devices fabricated from 1 or 2 [18].
the synthesis of 1,3,4-oxadiazole derivatives 15b–g with antici-
pated semiconducting and photoluminescent properties. First,
alkaline hydrolysis of the esters 7b–g led to the corresponding
carboxylic acids 12b–g in good yields (70–87%, Scheme 3).
Results and Discussion
Synthetic toolbox
It is well known that thiophenes containing acceptor groups The corresponding hydrazide derivatives 13b,c were obtained in
such as CHO, CN or CO2Me at the C-2 position readily react 67–73% yields by refluxing the esters 7b,c with hydrazine
with aryl halides in the presence of a Pd(II) catalyst through a monohydrate in alcohol. The diacyl hydrazines 14b,c were ob-
Heck-type coupling [26]. We have synthesized the ethyl ester of tained through the coupling of the hydrazide derivatives 13b,c
2,2'-bithiophene-5-carboxylic acid 7a [25] to study its reactivi- with carboxylic acids 12b,c in the presence of N,N'-dicyclo-
ty towards various aryl halides, namely: iodobenzene (8), hexylcarbodiimide (DCC) as reported earlier [18]. A modified
1-bromonaphthalene (9) and the 9-bromanthracene (10) and procedure, which avoids the preparation of hydrazides 13, was
1-bromopyrene (11) (see Scheme 2).
used for the synthesis of 14d–g. These intermediates were syn-
thesized by the reaction of the acid chlorides with hydrazine
Initial attempts to carry out the reaction under the same condi- dihydrochloride in the presence of pyridine. The required acid
tions as described in [26], i.e., heating a mixture of 7a with 8 or chlorides were prepared in situ through the reaction of the cor-
9 in dimethylacetamide in the presence of Pd(OAc)2, Bu4N+Br− responding carboxylic acids 12b–g with oxalyl chloride. The
and K2CO3, led to inseparable mixtures. Further, compounds yields of the obtained diacylated hydrazines 14b–g were in the
7d–g could not be isolated when the base K2CO3 was replaced range of 58–74% (Scheme 3).
with Cs2CO3 and PPh3 was used as a ligand [27]. Gratifyingly,
the 5'-arylated products 7d–g were obtained by heating a mix- Finally, heating the diacyl hydrazines 14b–g in phosphorus
ture of ethyl 3-decyl-2,2'-bithiophene-5-carboxylate (7a) with oxychloride led to the formation of the desired 1,3,4-oxadia-
aryl halides in the presence of tetrakis(triphenylphosphine)- zoles 15b–g. The product yields were between 65–94% after
palladium(0) and AcOK in DMF for 20–22 h. Unfortunately, purification by column chromatography (Scheme 4).
Scheme 2: Synthesis of ethyl esters of 5'-aryl-3-decyl-2,2'-bithiophene-5-carboxylic acids 7d–g.
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Table 1: Reaction conditions and yields for the synthesis of ethyl 5'-aryl-3-decyl-2,2'-bithiophene-5-carboxylates 7d–g.
Entry
Compound
Reaction conditions
Yield, %
18
DMF, AcOK, 130 °C, 55 h,
Pd(PPh3)4
1
7d
7e
DMF, AcOK, 130 °C, 28 h,
Pd(PPh3)4
2
3
60
49
DMF, AcOK, 130 °C, 20 h,
Pd(PPh3)4
7f
DMF, AcOK, 130 °C, 23 h,
Pd(PPh3)4
4
42
7g
Scheme 3: Synthesis of diacyl hydrazines 14b–g.
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Beilstein J. Org. Chem. 2017, 13, 313–322.
Scheme 4: Synthesis of 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles 15b–g.
All intermediates and final products were identified by tive (389 nm). The largest shift of λmax is observed in the spec-
elemental analysis, NMR and IR spectra, which are presented in tra of the 5’-thienyl- (409 nm), 5’-phenyl- (403 nm) and
Supporting Information File 1.
5'-pyrenyl (406 nm) derivatives 15c,d,g (Table 2).
Spectroscopic and luminescent properties of
the synthesized compounds
As evidenced by the data presented in Table 2, the optical band
gaps (ΔEgopt) for the synthesized oxadiazole derivatives are
The 1,3,4-oxadiazole derivatives 15b–g are powders of yellow almost independent of the carboaromatic substituents’ size.
to orange color and their solutions exhibit fluorescent proper- However, in all cases they are lower than the band gap of the
ties. The absorption and fluorescence spectra registered for unsubstituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadi-
dichloromethane (DCM) solutions are presented in Figure 2 and azole (2.87 eV) [16] and of the 5'-alkyl-substituted derivative
the obtained spectral parameters are collected in Table 2.
15b (2.81 eV). This rather weak dependence of the band gap on
the aromatic substituent size observed for compounds 15d–g,
All compounds display an intense absorption band with a can be explained by two opposite effects which partly compen-
maximum between 389 and 409 nm, ascribed to the π–π* transi- sate each other: larger substituents increase the number
tion. A comparison of the absorption spectra of 15b and 15c–g of π-bonds being in conjugation but at the same time
indicates that the presence of a thiophene ring or carboaromatic they induce non-planarity due to steric hindrance, which
substituents at the C-5' position in the 2,5-bis(2,2'-bithiophen-5- lowers the effective conjugation. This problem will be
yl)-1,3,4-oxadiazole leads to a slight bathochromic shift of the discussed in detail in the section devoted to quantum chemical
absorption band as compared to the corresponding alkyl deriva- calculations.
Figure 2: 5'-Aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles 15b–g: a) absorption spectra, b) photoluminescence spectra in
DCM.
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Table 2: Spectroscopic and luminescent properties of 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles 15b–g in DCM.
Compound
UV–vis
photoluminescence
Stokes shifte Δ
λmax,absa Egopt b
λexc
λmax,emd
ФFf
[nm]
[eV]
[nm]
[nm]
[nm]
[eV]
389
2.81
377
396
390
448; 472
59
0.52
0.84
15b
409
403
2.62
2.69
484; 507
468; 496
75
65
0.57
0.53
0.20
0.49
15c
15d
397
395
2.74
2.78
381
372
473; 496
76
0.63
0.85
0.25
0.18
15e
499
104
15f
406
2.63
380
501
95
0.79
0.29
15g
aAbsorption, bpertaining to onset of the π–π* absorption peak, cexcitation, demission, eminimum value, fquantum yield determined relative to
9,10-diphenylanthracene as the standard.
When excited by UV light, all studied compounds emit blue the largest substituents anthracen-9-yl (0.85 eV) and pyren-1-yl
(468, 473 nm) or bluish-green (499, 501) light (Table 2). Mod- (0.79 nm), respectively. Note the clear vibrational structure in
erate to large values of Stokes shifts are observed for com- the spectra of 15b–e which is nonexistent in the case of 15f,g
pounds 15b–g originating from bond order switching (Figure 2). The measured photoluminescence quantum yields
(benzenoid to quinoid) in the excited state. Moderate values of decrease in the following order: 15b (0.84) > 15d (0.49) > 15g
Stokes shifts (0.52–0.63 eV) are observed for 15b–e and the (0.29) > 15e (0.25) > 15c (0.20) ≈ 15f (0.18), indicating that for
Stokes shift increases with an increase of the aryl substituent larger substituents the non-radiative rate constant increases.
size. As expected, the largest Stokes shift values of 0.85 eV and Such phenomena are frequently observed in D–A–D-type
0.79 eV are observed for 15f and 15g, i.e., the derivatives with conjugated molecules [28].
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Beilstein J. Org. Chem. 2017, 13, 313–322.
DFT calculations
observed for derivatives with substituents of increasing size.
To gain a deeper understanding of the electronic and photo- Thus, 15e can exist in two conformations with different orienta-
physical properties of the synthesized 5'-aryl-substituted 2,5- tion of the terminal substituents with respect to the central core.
bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles we have At the same time, unsymmetrical substituents lead to additional
performed quantum-chemical calculations for four derivatives conformational variety, e.g., the naphtalen-1-yl-substituted de-
having a thienyl (15c), phenyl (15d), naphthalen-1-yl (15e) and rivative 15e can be represented by five different conformers.
anthracen-9-yl (15f) aromatic substituent. The DFT/TDDFT ap- Table 3 collects selected geometrical parameters for the studied
proach at the B3LYP/Def2-SVPD level of theory coupled with conformers, whereas their graphical representations are shown
polarizable continuum model of solvent effects and using the in Figure 3 (detailed geometrical structures of the studied com-
integral equation formalism variant (IEFPCM) was applied. pounds 15c–f are shown in Supporting Information File 1,
Figure 3 shows a general representation of the compounds Figure S2).
studied in this work.
For derivatives 15c and 15d in which the substituent consists of
one aromatic ring, the whole 1,3,4-oxadiazole molecule is flat,
since the dihedral angles D1, D2 and D3 are very close to zero.
However, in case of 15e and 15f a substantial non-planarity is
induced by the larger substituents as evidenced by an increase
of their dihedral angles values. Note, that the anthracenyl sub-
stituent is almost perpendicular to the adjacent thienylene ring
(D1 is approximately 88°) [29]. This dihedral angle is “a
Figure 3: General structure of 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-
bithiophen-5-yl)-1,3,4-oxadiazoles.
compromise” between the conjugation of the adjacent segments
which favors the molecule’s planarity and steric hindrance
effects which induce torsion. In the case of larger sized substitu-
At the initial stage, a systematic conformational analysis of the ents, the steric effect predominates leading to large values of
series of substituted 1,3,4-oxadiazoles was conducted with the dihedral angles and limiting the conjugation to the substituent
goal to determine the lowest-energy conformer(s). It has been itself. It is worth mentioning, that the size of the aryl substitu-
found that 15c and 15d can exist only as a single conformer of ents also affects the whole molecule’s geometry since D2 and
planar structure. An increasing conformational variety has been D3 angles also increase for larger substituents.
Table 3: Selected geometrical parameters (bond lengths, B and dihedral angles, D) for all found conformers of the studied compoundsa, as well as
relative energies, Erel, for each conformer in the ground state obtained for DCM solution (IEFPCM) at the B3LYP/Def2-SVPD level of theory.
№
Dihedral Angle (D), degree
Bong length (B), Å
B1
Relative energy (Erel)
kcal/mol
|D1|
|D2|
|D3|
B2
B3
15c
15d
15e
0.01
0.01
0.00
0.01
0.01
0.00
1.4495
1.4691
1.4477
1.4484
1.4362
1.4363
Erel = 0
Erel = 0
Conformer SS1
55.84
6.71
0.34
0.08
0.59
0.31
1.4770
1.4774
1.4771
1.4749
1.4749
1.4842
1.4842
1.4504
1.4505
1.4503
1.4499
1.4501
1.4531
1.4515
1.4353
1.4366
1.4366
1.4365
1.4566
1.4374
1.4367
Erel = 1.07
Erel = 1.05
Erel = 0.57
Erel = 0.11
Erel = 0
Conformer SS2
57.18
3.30
Conformer AS
56.31
0.16
Conformer AA1
47.24
9.80
Conformer AA2 (most stable)
47.54
Conformer A
88.62 22.34
13.33
1.35
15f
0.20
Erel = 0.13
Erel = 0
Conformer S (most stable)
88.64 8.05 0.85
an-Decyl groups in the compounds were replaced with CH3 throughout to simplify the calculations.
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Beilstein J. Org. Chem. 2017, 13, 313–322.
DFT and TDDFT approaches have proven to be very efficient state geometry optimization, i.e., B3LYP/Def2-SVPD/
and versatile tools for the investigation of both ground and IEFPCM(DCM). However, the obtained excitation energies
excited-state properties of various organic and inorganic com- revealed an extremely poor agreement between the quantum-
pounds [30,31]. However, it has been shown that the descrip- chemical predictions and the experiment. According to the theo-
tion of π–π* transitions for bithiophene derivatives of 1,3,4- retical results the observed transition is solely connected with
oxadiazoles still remains challenging. Grimme and Dierksen the HOMO–LUMO transition. A careful analysis of frontier
[32] have demonstrated that calculations performed by the molecular orbitals disclosed a notable charge transfer from the
hybrid B3LYP functional with a triple-ξ quality basis set almost central part to the terminal substituents (Figure 4).
perfectly describe singlet–singlet π–π* transitions for
2,2':5',2'':5'',2''':5''',2''''-quinquethiophene and 2,5-diphenylfuran. Considering the fact that the non-coulombic part of hybrid func-
They have further demonstrated that the basis set of double-ξ tionals typically dies off too quickly resulting in lack of preci-
quality shows a small decrease of the displacement of the ob- sion at large distances and lack of suitability for some tasks as-
tained spectrum compared to triple-ξ quality, while the larger sociated with electron-excitation modeling, we repeated our
basis sets yield almost identical results. The hybrid B3LYP calculations with the range-separated hybrid CAM-B3LYP
functional coupled with an integral equation formalism of the functional. Indeed, the CAM-B3LYP functional provides values
polarizable continuum model (IEFPCM) provides a reasonable of the transition energies which are well correlated with the ex-
and qualitatively adequate description of vertical excitation pro- perimentally measured optical band gap (determined from the
cesses for bithiophene derivatives of 1,3,4-oxadiazoles [21].
absorption spectrum). The analysis of vertical excitation shows
that several molecular orbitals are involved in this process, but
The absorption spectra of the investigated compounds measured the main contribution (estimated by coefficients of the wave
in DCM demonstrate a featureless band with maxima allocated function for each excitation) comes from the HOMO–LUMO
in the range from 395 to 409 nm. The maximum of absorption (predominantly) and HOMO−1–LUMO+1 transitions. For thio-
ascribed to the π–π* transition for the studied thiophene, phen- phene-substituted derivatives, the HOMO is delocalized over
yl, naphthalene and anthracene-substituted derivatives, shows a the whole molecule, while the LUMO is mostly presented in the
small hypsochromic shift with increasing spatial volume of the central part of molecule. In turn, for the other examined mole-
substituent R. This observation is in a full accordance with the cules, the situation is more or less reverse. The HOMO is local-
aforementioned relationship of the molecule planarity and aro- ized mainly in the central part of molecules (central core), while
matic conjugation.
the LUMO is concentrated on the substituents R with a small
electron density on the 1,3,4-oxadiazole fragment (Figure 4).
Initially, for optical transition simulations, we have used the The peculiarity of the HOMO–LUMO localization for thio-
same functional and basis set as has been used for the ground phene and phenyl substituents can be rationalized taking into
Figure 4: Frontier molecular orbitals (HOMO−1, HOMO, LUMO and LUMO+1) and values for HOMO–LUMO band gaps of the investigated mole-
cules calculated at the IEFPCM(DCM)-CAM-B3LYP/Def2-SVPD level of theory. The isovalue of each depiction is equal to 0.03 e/au3.
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To summarize, we have shown that ethyl esters of 5'-aryl
3-decyl-2,2'-bithiophene-5-carboxylic acids can be prepared by
the palladium-catalyzed coupling of readily available com-
pounds, namely ethyl 3-decyl-2,2'-bithiophene-5-carboxylate
and aryl halides. Using these building blocks the synthesis of
new fluorescent conjugated 5'-aryl-substituted 2,5-bis(3-decyl-
2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles was developed. DFT
calculations of the 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-
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Supporting Information File 1
Experimental, computational and analytical data
[http://www.beilstein-journals.org/bjoc/content/
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A. S. F. and A.S. K. acknowledge partial financial support from
the Russian Foundation for Basic Research (15-43-04313-
Sibiria-a; 16-33-00340 mol_a) and the Ministry of Education
and Science of the Russian Federation (the Agreement number
02.a03.21.0008). A. J. S. gratefully acknowledges The Interdis-
ciplinary Centre for Mathematical and Molecular Modelling of
the University of Warsaw (ICM) for computational facilities
(grant no. G-33-17). Support of the Faculty of Chemistry of
Warsaw University of Technology is acknowledged by A.P.
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