Synthesis of Perylene Imide Diones as Platforms for the Development of Pyrazine Based Organic Semiconductors

Article abstract of DOI:10.1021/acs.joc.6b02214

There is a great interest in peryleneimide (PI)-containing compounds given their unique combination of good electron accepting ability, high abosorption in the visible region, and outstanding chemical, thermal, and photochemical stabilities. Thus, herein we report the synthesis of perylene imide derivatives endowed with a 1,2-diketone functionality (PIDs) as efficient intermediates to easily access peryleneimide (PI)-containing organic semiconductors with enhanced absorption cross-section for the design of tunable semiconductor organic materials. Three processable organic molecular semiconductors containing thiophene and terthiophene moieties, PITa, PITb, and PITT, have been prepared from the novel PIDs. The tendency of these semiconductors for molecular aggregation have been investigated by NMR spectroscopy and supported by quantum chemical calculations. 2D NMR experiments and theoretical calculations point to an antiparallel π-stacking interaction as the most stable conformation in the aggregates. Investigation of the optical and electrochemical properties of the materials is also reported and analyzed in combination with DFT calculations. Although the derivatives presented here show modest electron mobilities of ～10^-4 cm²V^-1s^-1, these preliminary studies of their performance in organic field effect transistors (OFETs) indicate the potential of these new building blocks as n-type semiconductors.

Full text of DOI:10.1021/acs.joc.6b02214

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Article
Synthesis of perylene imide diones as platforms for the
development of pyrazine based organic semiconductors
Paula De Echegaray, Maria José Mancheño, Iratxe Arrechea-Marcos, Rafael Juárez, Guzmán López-Espejo,
Juan T. López Navarrete, Maria Mar Ramos, Carlos Seoane, Rocio Ponce Ortiz, and José Luis Segura
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02214 • Publication Date (Web): 19 Oct 2016
Downloaded from http://pubs.acs.org on October 19, 2016
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The Journal of Organic Chemistry
Synthesis of peryleneimidediones as platforms for the development of
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pyrazine based organic semiconductors
a
a
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c
Paula de Echegaray, María J. Mancheño, Iratxe ArrecheaꢀMarcos, Rafael Juárez, Guzmán Lópezꢀ
b
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b*
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Espejo, J. Teodomiro López Navarrete, María Mar Ramos, Carlos Seoane, Rocío Ponce Ortiz, José
a*
L. Segura
a
Departamento de Química Orgánica I. Facultad de Ciencias Químicas, Universidad Complutense de
Madrid, 28040 Madrid (Spain).
b
Departamento de Química Física, Facultad de Ciencias, Universidad de Málaga, 29071, Málaga
(
Spain)
c
Departamento de Tecnología Química y Ambiental, Universidad Rey Juan Carlos, Madrid 28933
Spain)
(
rocioponce@uma.es; segura@ucm.es
ABSTRACT. There is a great interest in peryleneimide (PI)ꢀcontaining compounds given their unique
combination of good electron accepting ability, high abosorption in the visible and outstanding
chemical, thermal and photochemical stability. Thus, herein we report the synthesis of perylene imide
derivatives endowed with a 1,2ꢀdiketone functionality (PIDs) as efficient intermediates to easily access
peryleneimide (PI)ꢀcontaining organic semiconductors with enhanced absorption crossꢀsection for the
design of tunable semiconductor organic materials. Three processable organic molecular
semiconductors containing thiophene and terthiophene moieties, PITa, PITb and PITT, have been
prepared from the novel PIDs. The tendency of these semiconductors for molecular aggregation have
been investigated by NMR spectroscopy and supported by quantum chemical calculations. 2D NMR
experiments and theoretical calculations points to an antiparallel πꢀstacking interaction as the most
stable conformation in the aggregates. Investigation of the optical and electrochemical properties of the
materials is also reported and analyzed in combination with DFT calculations. Although the derivatives
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ꢀ4
2
ꢀ1 ꢀ1
presented here show modest electron mobilities of ∼10 cm V s , these preliminary studies of their
performance in organic field effect transistors (OFETs) indicate the potential of these new building
block as nꢀtype semiconductors.
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KEYWORDS. peryleneimide, organic semiconductor, field effect transistor, DFTꢀcalculations,
pyrazine, thiophene.
Introduction
Organic electronics, which exploits organic molecular materials as semiconductors and active elements
1ꢀ8
in devices, is an important growing field of research. During the last decades, great effort has been
devoted to the design of both holeꢀconducting (pꢀtype) and electronꢀconducting (nꢀtype) organic
semiconductors, which are required for device applications. Although this research field has evolved
dramatically, the search of tunable organic molecules as nꢀtype organic semiconductors is still
challenging, due to the scarce molecular diversity of these materials, their limited device performance
compared to their pꢀtype homologues, their ambient instability and the lack of complete understanding
9ꢀ15
of electron transport.
Perylenediimides and naphthalenediimides (PDIs and NDIs) are two of the
most important families of nꢀtype semiconductors with multiple applications in organic field effect
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transistors (OFETs),
organic light emitting diodes (OLEDs)
or organic photovoltaic cells.
27,28ꢀ32
These rylene diimide systems have been proved to be robust, thermally stable and extremely
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versatile, since their electronic properties can be modulated by wellꢀestablished organic chemistry,
either through modifications on the rylene skeleton of through functionalization on the imide nitrogen
atom. In addition, they usually have high electron affinities, which is translated in most cases to
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remarkable electron transport properties. For example, NDI derivatives with fluorinated alkyl chains
have demonstrated to perform efficiently in air as nꢀtype semiconductors with mobilities of 0.12ꢀ0.57
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cm V s , while functionalization on the NDI core with electrowithdrawing groups, such as chloro
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or cyano,
renders also airꢀstable nꢀtype semiconductors with mobilities even surpassing 1 cm V s
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in thin film devices and up to 8.6 cm V s for single crystals NDIꢀFETs.
Similar electronic
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performances have been reported for PDI derivatives, with airꢀunstable fieldꢀeffect mobilities
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surpassing 2 cm V s for alkylꢀsubstituted PDIs and airꢀstable mobilities higher than 1 cm V s in
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the case of fluoroꢀalkyl substituted derivatives.
However, functionalization on the bay area of PDIs
have been less efficient than in NDIs due to distortion of the πꢀconjugated core, remaining only flat
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those systems substituted with cyano
and fluoro
groups. For this reason, the search of different
strategies to modulate the frontier molecular orbitals of PDIs is of prime interest. In this sense, in the
last few years we have synthesized oligothiopheneꢀnaphthalimide and peryleneimide assemblies with
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good performances in OFETs,
in which both donor and acceptor moieties are directly conjugated
through imidazole rigid linkers. It was found that the absence of skeletal distortions allows closer
intermolecular πꢀπ stacking and enhances intramolecular πꢀconjugation while distortion from planarity
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leads to interruption of the πꢀelectron orbital overlap and can adversely affect charge transport.
In
order to get planar analogues, we described the synthesis of a naphthalimide derivative endowed with a
1,2ꢀdiketone functionality (NID), as precursor of a family of oligothiopheneꢀnapthalimide assemblies
connected through pyrazine linkers (NIT, NI3T, Figure 1) with completely planar molecular skeletons,
which promote good film crystallinity and low reorganization energies for both electron and hole
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transport.
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Figure 1. Structure of Naphthalene imide dione (NID) and some derivatives obtained from this
diketone.
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Simultaneously, Jenecke and col. reported a synthetically tunable tetraazaanthracene core (BFI)
with two naphthalene imide units based in dione NID, creating large rigid ladderꢀtype structures as
promising nꢀtype materials for organic electronics and nonfullerene photovoltaics. New highꢀ
52
mobility n‑type conjugated polymers were also developed based on this versatile synthon.
Thus, in the search of larger planar building blocks with redꢀshifted absorption for the design of
tunable semiconductor organic materials, we describe in this communication the synthesis of PID
(Scheme 1), the first reported extension of a perylene diimide analogous to previously synthesized
naphthalene dione NID. The interest in perylenimide (PI)ꢀcontaining compounds is due to the unique
combination of good electron accepting ability, high absorption in the visible, and outstanding
chemical, thermal, and photochemical stability. Their extended aromaticity together with the
possibilities for functionalization make of them good candidates for potential applications in
31,53
electronic materials, sensors, and photovoltaics.
They also constitute accesible building blocks for
the synthesis of extended heteroacenes and heteroarenes, systems highly used in the last decade in
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thin film transistor with good performance. Herein, we report in detail the design, synthesis, and
structural characterization of two perylene imide diones (PID) with different substituents at the imide
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nitrogen and prove the potential of these building blocks, among others, for the synthesis of new
assemblies based on peryleneimides fused with electroactive moieties through pyrazine spacers.
Thus, new peryleneimides linked to thiophene and terthiophene moieties through pyrazine spacers
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(PIT and PITT) have been synthesized and the preliminary investigation of their optical and
electrochemical properties is presented.
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Results and discussion
As stated before, the synthesis of PIT and PITT was carried out starting from PIDs (Scheme 1).
Dione PIDa was synthesized by using the synthetic strategy depicted in Scheme 1. First, imide 2a
was obtained by reaction of anhydride 1 with 2ꢀethylhexylamine, in 98% yield. Alkyl chains in the
imide moiety were introduced for solubility purposes.
Scheme 1. General route to new perylene imide derivatives (PIT and PITT).
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The synthesis of monoimide 5 was carried out by two alternative procedures, based in palladium
catalyzed crossꢀcoupling reactions between brominated naphthalimides (2a,b) and either stannyl
derivative 3 or boronic acid derivative 4. The previously unknown acenaphthene 5ꢀtrimethyltin 3 was
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t
synthesized by reaction of 5ꢀbromoacenaphthene with BuLi and Me SnCl with high yield (95%).
3
On the other hand, boronic acid 4 was obtained also from 5ꢀbromoacenaphthene by treatment of the
organollithium derivative withtriisopropoxiborane and HCl (10%), in higher yield in comparison with
the procedure previously described (70% vs 45%).
Pd(PPh ) catalyzed Stille reaction between monostannane 3 and imide 2a in toluene afforded product
3 4
5
a in a very low yield. However, when the reaction was carried out in the presence of CuI and
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5
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CsF
(5% Pd(PPh ) , 20% CuI and 2 moles of anhydrous CsF) in DMF at 55ºC, 5a could be
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obtained in good yield (76 %). On the other hand, Suzuki reaction of boronic acid 3 in toluene with
the same catalyst led to precursor 5a with an even better yield (87%). Therefore, both methods are
feasible for the synthesis of derivative 5a.
Imide 5a was obtained as a bright yellow solid and was completely characterized by usual
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spectroscopic techniques. Its H NMR spectrum shows the characteristic singlet corresponding to the
methylene protons of the acenaphthene unit, and a multiplet assignable to the NꢀCH ꢀ of the alkyl
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chain at 4.34–4.02 ppm. The rest of aromatic and aliphatic protons are in the usual range. In the C
NMR it can be observed the presence of the two imide groups at 164.7 y 164.6 ppm.
For the synthesis of perylene derivative 6a we tested usual reaction conditions based in the use of
t
58ꢀ60
bases such as KOH, K CO /Ethanolamine, BuOK/DBN or DBU.
After several attempts using
2
3
different reaction conditions product 6a could be obtained with low yield (20%) by treatment of 5a
t
with BuOK/DBN at 140ºC. Product 6a was isolated from a complex mixture in which saponification
products of the imide could be detected, and therefore similar reaction conditions were tested using
61
the more robust Nꢀarylimide analogue 5b. Thus, imide 5b was obtained in a good yield by Suzuki
62
reaction of bromoderivative 2b with boronic acid 4 (Scheme 1). The subsequent treatment of 5b
t
with BuOK/DBN at 140ºC led only to perylenimide 6b in a 23% yield after silica gel
chromatography.
6
3,64,65,66
In view of these results, we turned our attention to the Scholl reaction
to perform the
cyclodehydrogenation process. The Scholl oxidation, which generates a new CꢀC bond between two
6
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unfunctionalized aryl carbon atoms, is known to be somewhat erratic. However, it has been
profusely used by Müllen and coworkers for the preparation of large polycyclic aromatic
65,68ꢀ71
hydrocarbons (PAHs) from branched polyphenylenes.
Thus, we first evaluated the common
72,73
reaction conditions (FeCl /acetonitrile)
with imide 5a but only oligomeric material could be
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isolated. Other reagents such as CuCl , Cu(OTf),
or DDQ/CH SO H did not produce detectable
3 3
2
quantities of the desired product. In our hands the best results were obtained by using AlCl . Reaction
3
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in refluxing toluene of either 5a or 5b with AlCl yielded after 3 h perylenes 6a and 6b with 30% and
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0% yield respectively, together with starting material (40 and 30% respectively) and oligomeric
fractions. The use of chlorobenzene instead of toluene as the solvent allowed increasing the yield of
Nꢀarylimide 6b (20%), with a 33% of recovered starting material. But, remarkably, imide 5a was
satisfactorily obtained under this reaction conditions with an excellent yield (80%), after column
chromatography.
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Both perylenes obtained 6a and 6b present quite good solubility in different solvents such as DCM,
chloroform, toluene, AcOEt or THF and could be characterized by spectroscopic and spectrometric
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methods. They exhibit similar features in their H NMR spectra. C NMR was carried out only on
perylene 6b and HRMS were satisfactory for both perylenes. Perylenes 6a,b were further oxidized
with benzeneseleninic anhydride (BSA) in chlorobenzene to afforddiones PIDs after chromatography
13
in good yield. Both diketones could be characterized by analytical and spectroscopic methods. C
NMR of compound PIDb was carried out in chloroform solution showing the carbonyl and imide
groups at 187.2 and 163.6 ppm respectively.
Diketones PIDs represent unique and versatile building blocks for the design of new πꢀconjugated,
electroactive and multichromophoricsystems for optoelectronic applications. In this context, fusedꢀ
ring thieno[3,4ꢀb]pyrazines have been shown to be suitable monomeric unitsin low band gap
7
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conjugated polymers.
Thus, we choose the condensation reaction between PIDs and
diaminothiophene derivatives to check the potential of the novel building blocks for the synthesis of
new assemblies based onperyleneimides fused with thiophenemoieties through pyrazine spacers.
Peryleneꢀoligothiophene assemblies PITa, PITb and PITT were obtained by reaction of diketones
PIDs with the corresponding diamine derivative in chloroform solution. All compounds were
partially soluble in chlorinated solvents such as DCM, chloroform, chlorobenzene, dichlorobenzene
1
and nonꢀsoluble in polar solvents such as acetonitrile and MeOH. As characteristic, H NMR spectra
of PIT compounds exhibit at 7.96 ppm the singlet of the thiophene moiety. For all of them aromatic
1
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protons appear as broad signals in the usual range. C NMR could only be obtained of PITb.
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However, additional analytical evidence for these novel systems was provided by high resolution
mass spectrometry.
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The optical and electronic properties of the novel fused thieno[3,4ꢀb]pyrazines PITs and PITT have
beenanalyzed by UVꢀVisible spectroscopy, cyclic voltammetry and theoretical calculations.
Naphthalimides NITs (NITa, R = C H and NITb, R = C H , Figure 1) have been also synthesized
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as previously described by some of us
and included in this study for comparison purposes. (See
all figures in SI). The UVꢀvis spectra of PITa and PITb in different solvents show identical features
regardless of the substituents on the imide N atoms (Figure 2). Both PIT derivatives exhibit the
characteristic absorption of perylene imide moieties with maxima at 507 nm and 545 nm that can be
ascribed to the 0–0 and 0–1 vibronic band of the S0–S1 transition respectively, while the observed
absorption band with maxima at 476 nm is attributed to the electronic S0–S2 transition. These
absorptions are significantly red shifted in comparison with that of naphthalimide analogues (NIT)
with a maximum of the lowestꢀenergy absorptium band at 450 nm. The UVꢀvis spectrum of PITT is
especially remarkable. It presents maxima at 342 and 383 nm together with the above mentioned
perylene imide bands at 511 and 555 nm but, in addition it exhibits a broad absorption centered at
approximately 668 nm that extends up to 900 nm and which can be assigned to an intramolecular
chargeꢀtransfer (ICT) excitation (Figure 2).
Figure 2. left: UVꢀVis absorption spectra of PIT, NIT and PITT in DCM. right: comparative
voltamperogramms of PITb and NITb. Cyclic voltammetry in DCM/TBAPF6 (0.1 M) at a scan rate
+
of 100 mV/s using Pt as working and counter electrode, and Fc/Fc as reference.
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PITa
NITb
PITb
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1,0
PITb
NITa
PITT
6
4
2
0
2
O
N
O
0,8
0,6
0,4
0,2
O
N
O
N
N
-
S
-4
N
N
-6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-8
S
-10
0,0
3
-
12
00
400
500
600
700
800
900
-2,5
-2,0
-1,5
-1,0
-0,5
0,0
1
/2
λ
(nm)
E
vs
E
(V)
Fc/Fc+
The redox behavior of the novel systems was investigated by cyclic voltammetry (CV) measurements
Figure 2 and Figures 7ꢀ11 in supporting info). Both PIT exhibit two reversible reduction processes,
(
due to theperylene imide moiety, within the solvent/electrolyte window range. In contrast, PITT
displays quasiꢀirreversible reduction waves. From these data, together with the onset of the
absorption spectra, the LUMO and HOMO energies were estimated using standard approximations
and compared with that obtained from theoretical calculations (see Table 1 and SI for details). Thus,
by comparing PITb derivative with the naphthalene imide analogue NITb (Table 1), as
representative, it is observed that the LUMO energies are only slightly affected by the increasing of
the core size. Therefore, the HOMO−LUMO gap decrease is associated with the destabilization of the
HOMO in PIT derivatives with a larger πꢀconjugated skeleton. On the other hand, oligothiopheneꢀ
perylene PITT presents a similar LUMO energy level but the HOMO level is more destabilized as
the oligothiophene fragment is extended.
[a]
Table 1. UVꢀvis absorption and electrochemistry data
ꢋ
e
OP
b
c
ꢅ/ꢆ
ꢂꢃꢄ
V)
ꢅ/ꢆ
ꢇ
ꢌꢇ
ꢈꢉꢊ
EGAP
LUMO
(eV)
HOMO
(eV)
ꢀꢁ
(
ꢀ
(V)
ꢈꢉꢊ
ꢁꢂꢃꢄꢄ
ꢀ1 ꢀ1
(nm)
(V)
(
cm M )
4
PITb
NITb
PITT
ꢀ1.04
ꢀ1.28
545
336
383
1.21 10
5.12 10
1.94
ꢀ3.40
ꢀ5.34
(ꢀ5.64)
ꢀ6.00
(
(
(
ꢀ3.18)
5
ꢀ0.95
ꢀ1.33
ꢀ1.41
2.51
1.43
ꢀ3.49
ꢀ3.01)
ꢀ3.33
ꢀ3.19)
(ꢀ6.22)
ꢀ4.76
d
3
ꢀ1.11
9.1 10
(ꢀ5.03)
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[a] Cyclic voltammetry in DCM/TBAPF6 (0.1 M) at a scan rate of 100 mV/s using Pt as working and counter electrode, and SCE as reference (0.52 V
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
+
OP
vs Fc/Fc ). [b] LUMO level estimated versus the vacuum level from ELUMO=ꢀ4.44 eVꢀeEred1. [c] Estimated from HOMO=LUMOꢀEGAP
DFT//B3LYP/6ꢀ31G** theoretical data are shown in brackets). [d] Ered Irreversible. [e] Calculated with a linear regression to Lambert Beer law.
.
(
These results can be rationalized in terms of the different topologies of the frontier orbitals. Note that
the LUMOs are more localized at the ryleneimide moieties whereas the HOMOs are localized over
the entire molecular πꢀframeworks (Figure 3). In the case of PITT, HOMO is localized primarily on
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
9
the oligothiophene chain as for previously described NI3T derivative.
Figure 3. B3LYP/6ꢀ31G** optimized structures for NITb (Top left), PITb (Mid. left) and PITT
(Down left), and respective HOMO (center) and LUMO (right) computed orbital topologies.
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1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
It is worth pointing out that the LUMO values determined for PIT and PITT derivatives are
7
9
comparable to those of stateꢀofꢀtheꢀart nꢀtype semiconductors. In fact, we already reported that NIT
4
9,50
derivatives with analogous LUMO values behaved as nꢀtype semiconductors in OFETs.
Interestingly, as the HOMO levels of PIT derivatives are destabilized in comparison with that of the
parent NIT analogues (1.94 V vs 2.51e.V), they approaches the Fermi level of Au (5.0 eV), which is
beneficial for hole injection and can pave the way for the development of a new family of ambipolar
semiconductors when combined with suitable moieties.
In this respect, the internal reorganization energies, λ, for both electron and hole transport in PIT and
80
PITT derivatives have been computed as previously described and compared with that of NIT and
NI3T analogues. A λ of 0.25 and 0.20 eV was determined for PIT derivatives which are slightly
e
smaller than the value of 0.34 eV calculated for NIT. More similar values are obtained for PITT and
NI3T (λ of 0.24 vs 0.25). This behavior is in agreement with that previously observed for us in other
e
46
thiopheneꢀnaphthalimide and thiopheneꢀpeyleneimide assemblies. Furthermore, a λ as low as 0.10
h
eV was determined for PITa while a value of 0.16 eV was previously reported for the NIPa
4
9,50
analogue.
Thus, the extension of the πꢀconjugated system while keeping a fully planar structure
provides low reorganization energies for these new perylene imide derivatives.
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We have also explored the molecular aggregation behavior of the novel perylene derivatives.
Molecular aggregation in solution, preferentially by πꢀstacking, is a highly desired property for
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
8
1
potential use of these compounds in organic electronics and we now address this issue. Aggregation
can be experimentally studied, among others, by scanning the dependence of the absorption and
NMR spectra as a function of concentration. In the concentration range available for UVꢀvis
measurements, no significant change was observed for these derivatives. However, at the higher
concentrations (0.3ꢀ6 mM) used for NMR experiments carried out at 25 ºC, aggregation dependent
NMR spectra were observed, being this behavior specially significant for perylene derivatives 6a and
PITa. Thus, increasing sample concentrations lead to a significant shield of the aromatic protons as
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
well as the methylenes of the acenaphthene unit (Figure 4).
1
Figure 4. HꢀNMR spectra (300 MHz, CDCl ) of the aromatic region of 6a (left) and PITa (right) in
3
CDCl solutions at different concentrations.
3
Further insight into the selfꢀaggregation behavior of PITa and most probable sites of interactions was
provided by 2D NMR Overhauser effect enhancement (NOESY) (Figure 5). NOESY cross peaks
clearly indicate proximity of the aromatic protons of the perylene and the thiophene moieties to the
CH and CH of the Nꢀalkyl branched chain. Cross peaks of perylene d protons with the alkyl chain
2
protons (e and f) can be due to intramolecular interaction because the distance between them is
shorter than 5Å as predicted by computational model, but the other crossꢀpeaks between e, f and a, b
c protons must be explained by selfꢀaggregation.
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1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 5. Expansion of NOESY spectrum (700 MHz, CDCl , 6 mM) of PITa
3
This spectroscopic finding is in line with the theoretical data obtained on dimer assemblies. Thus, we
have theoretically explored the molecular aggregation of the novel perylene derivatives by using ab
initio (in all cases a B3LYP functional and 6ꢀ31G** basis were used) calculations on dimer models
where the alkyl chains were substituted by hydrogen atoms. Two πꢀstacking conformations (parallel
and antiparallel) and three displacement directions (x, y and z axis) were considered (Figure 6).
Figure 6. Top: Different conformations of dimers of the model PIT with hydrogen atoms instead of
alkyl chains. Middle: Pure parallel and antiparallel conformation dimer relative energies (zꢀaxis only
displacement). Bottom: 2D energy surfaces of antiparallel dimer conformations (z and y axis
displacement). (B3LYP/6ꢀ31G**).
z-axis displacement
y-axis displacement
Parallel
Antiparallel
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100
10
1
2
3
4
5
6
7
8
9
9
8
7
0
0
0
8
NIT-H
PIT-H
PITT-H
Bisimide 6-H
NIT-H
PIT-H
PITT-H
Bisimide 6-H
Parallel dimers
6
Antiparallel dimers
4
2
60
50
40
30
0
-2
-4
-6
-8
-10
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
20
10
0
3
4
5
6
7
8
9
10
4
5
6
7
8
9
10
z-axis Displacement ( )
z-axis displacement ( )
Dimer relative
energy (KJ/mol)
5
.0
.8
.6
.4
.2
.0
.8
.6
.4
.2
5.0
4.8
4.6
4.4
4.2
4.0
3.8
3.6
3.4
3.2
Bisimide 6-H
NIT-H
-11.00
4
4
4
4
4
3
3
3
3
-
10.00
-9.000
-8.000
-
-
7.000
6.000
-5.000
-
-
4.000
3.000
-2.000
-1.000
0.000
1.000
-5
-4
-3
-2
-1
0
1
2
3
4
5
-5
-4
-3
-2
-1
0
1
2
3
4
5
5.0
4.8
4.6
4.4
4.2
4.0
5.0
4.8
4.6
4.4
4.2
4.0
3.8
3.6
3.4
3.2
PITT-H
PIT-H
2
3
4
5
.000
.000
.000
.000
6.000
7.000
3
3
3
3
.8
.6
.4
.2
8
9
1
.000
.000
0.00
-5
-4
-3
-2
-1
0
1
2
3
4
5
-5
-4
-3
-2
-1
0
1
2
3
4
5
y-axis displacement (Å)
Calculations predict that antiparallel dimer is the most stable conformer, showing no minima in the
case of parallel conformer (even when yꢀaxis displacement is considered). The energy profiles
depicted in Figure 6 predict that the pure antiparallel πꢀstacking interaction is the most stable
conformation in NIT and PITT molecules (ꢀ5.2 and ꢀ6.3 KJ/mol respectively), while the most stable
conformation for imide 6 and PIT (ꢀ11.5 and ꢀ3.2 KJ/mol respectively) is found when one of the
units of the dimer is slightly yꢀaxis displaced (Table 2).
Table 2. Calculated intermolecular distance and energies for the dimers of the model compounds.
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Model
Compounds
Bisimide 6-H
Vertical
displacement (Å)
Horizontal
displacement (Å)
±1.5
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Energy (KJ/mol)
4
ꢀ11.5
NIT-H
PIT-H
4.0
4
0
±2.5
0
ꢀ5.2
ꢀ3.2
ꢀ6.3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
PITT-H
4.1
In order to unambiguously determine the selfꢀaggregation of PITa, additional calculations were
performed, taking into account the interactions observed in its 2D NOESY. In such twoꢀdimensional
NMR spectra throughꢀspace interactions at proximities of 5 Å or less are observed and are
particularly useful for determining the structure of aggregates in solution, so the starting point in
these calculations was a zꢀaxis distance of 4 Å for the PIT-H model. Parallel and antiparallel
conformations energies of PIT-H dimers were also calculated when a certain xꢀaxis displacement is
present (Figure 7). Results show that parallel displaced PIT-H dimer (xꢀaxis displacement between 6
and 8 Å) is barely stabilized, less than 1 KJ/mol. However, for the antiparallel dimer two stability
zones were found, the first one corresponds to the pure antiparallel dimer (xꢀaxis displacement equal
to 0) and the second one is observed when the xꢀaxis is displaced in the 7.5 to 10 Å range (Figure 7).
Assuming these theroretical models, the only aggregated structure, that could explain the NOE effect
observed, corresponds to an antiparallel mode of aggregation, where the distances between the imide
hydrogen and the hydrogens b and c of the perylene vicinal unit are in the NOE range.
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Figure 7: Left: Relative energy of parallel and antiparallel PIT-H dimers when a xꢀaxis displacement
is performed. Right: Dotted lines represent distances between 4.5 and 5.5Å. (top) parallel stable
conformation, (mid. and down) most stable antiparallel conformations.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
1
1
1
6
4
2
0
8
6
4
2
0
2
4
PIT-H antiparallel
PIT-H parallel
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-
-
0
1
2
3
4
5
6
7
8
9
10
11
x-axis displacement (Å)
OFET fabrication and characterization
Bottomꢀgate topꢀcontact OTFTs were fabricated using the studied molecules as the active layer. Gate
dielectrics (pꢀdoped Si wafers with 300 nm thermally grown SiO dielectric layers) were
2
functionalized either with hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS) selfꢀ
ꢀ2
assembled monolayers. The capacitance of the 300 nm SiO gate insulator was 10 nFcm . Prior to
2
the surface functionalization, the wafers were solvent cleaned by immersing them twice for 30
seconds each in EtOH with sonication, drying with a stream of N , and treating with UVꢀozone for 10
2
min. The cleaned silicon wafers were treated with hexamethyldisilazane (HMDS) by exposing them
to HMDS vapor at room temperature in a closed airꢀfree container under argon, and were treated with
octadecyltrichlorosilane (OTS) by inmersion in a 3.0 mM humidityꢀexposed OTSꢀhexane solution for
8
2
1
h, as previously described. Following OTS deposition, the substrates were sonicated with hexane,
acetone, and ethanol, and dried with a N stream. Data obtained is collected in Table 3.
2
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Table 3. OFET electrical data for vaporꢀdeposited films (unless otherwise specified) of the indicated
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
semiconductors measured in vacuum.
[a]
2
ꢀ1 ꢀ1
Subst. /T (ºC)
ꢀ (cm V s )
V (V)
T
e
ꢀ
5
PITa
PITa
PITa
PITb
PITT
H/110
5.8×10
1.5×10
1.1×10
1.2×10
1.2×10
31
36
33
25
8
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ꢀ4
O/150
ꢀ4
H/150
ꢀ4
ꢀ4
O/110
[
b]
O/SPꢀ130
[
[
a]
H: hexamethyldisilazaneꢀtreated substrates, O: nꢀoctadecyltriꢀchlorosilaneꢀtreated substrates.
b]
SP: solutionꢀprocessed film.
Next, the semiconductors were either dropꢀcasted or vaporꢀdeposited on preheated substrates. After
semiconductor deposition, the solutionꢀprocessed films were annealed under vacuum at selected
temperatures, and initially analyzed by AFM techniques (Figure 8). OFET devices were completed
by gold electrodes vapor deposition through a shadow mask to define devices with various channel
lengths and channel widths. Devices were characterized under vacuum and ambient conditions inan
EBꢀ4 Everbeing probe station with a 4200ꢀSCS/C Keithley semiconductor characterization system.
Figure 8. AFM images (5×5ꢀm) of thin films of the studied semiconductors deposited on substrates
preheated at the indicated temperatures.
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The Journal of Organic Chemistry
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Figure 8 shows AFM images for PITa and PITb thin films deposited onto HMDS or OTS treated
substrates preheatedat selected temperatures. In the case of PITa, we observe that grain sizes are
strongly dependent on the deposition temperature. While small rounded grains are recorded for films
annealed at 110 °C, grain sizes of around 0.5ꢀm are found at higher annealing temperatures. Note
however that the grain connectivity is poor for 150 °C annealed films. Although the morphology is
still far away from optimum, the substitution of the alkyl chain of PITa by a phenyl unit, PITb,
results in wellꢀdefined rounded grains presenting better connectivity. The most noticeable
morphology change is recorded for the solution processed film of PITT, where rodꢀlike grains
surpassing 1ꢀm are observed. These morphology changes parallel those previously recorded for their
homologous NIT and NI3T derivatives, where rodꢀlike grains are also found for the terthiophene
49
derivative deposited at high temperatures.
Figure 9. Output plots for vaporꢀdeposited PITa FETs grown at 150ºC on HMDSꢀtreated substrates
(left), and vaporꢀdeposited PITb FETs grown at 110ºC on OTSꢀtreated substrates (right).
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Comparing the electrical performances of vaporꢀdeposited films of the studied semiconductors in a
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OFET geometry (Figure 9), we observe a clear enhancement of the electron field effect mobility (×2)
ꢀ4
2
ꢀ1 ꢀ1
ꢀ5
2
ꢀ1 ꢀ1
of PITb (1.2×10 cm V s ) respect to PITa (5.8×10 cm V s ) when deposited on substrated
preheated at 110ºC. This can be ascribed to formation of rounded wellꢀconnected grains in the
former, as evidenced by AFM images. Higher substrate temperature while deposition increases PITa
mobility to similar values of those recorded for PITb. This electrical performance is comparable with
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previously published for NIT semiconductors.
In the case of the terthiophene derivative, films were deposited by drop casting; devices with
ꢀ4
2
ꢀ1 ꢀ1
electron mobilities of 1.2×10 cm V s were registered. However, despite the presence of the
terthiophene moiety, no ambipolar behavior is observed for PITT which contrasts with that observed
47
for other donorꢀacceptor assemblies containing terthiophenemoieties. This fact can be rationalized
in terms of the antiparallel πꢀπ stacking conformation of the novel molecules anticipated by
theoretical calculations and empirically observed, which does not allow to form D and A domains for
83
transporting holes and electrons, respectively.
Conclusions
In conclusion, the methodology described in this paper constitutes an efficient strategy for the
synthesis of perylene imide diones PID as reactive intermediates for the development of new
pyrazine fused πꢀconjugated systems with good electron accepting ability and high absorption in the
visible region. Especially noteworthy is the UVꢀvis absorption of the assembly based on
perylenimide and terthiophene which shows an enhanced absorption cross section from 300 to 900
nm. Aggregation dependent NMR spectra were obtained thus confirming the characteristic tendency
for molecular aggregation through πꢀπ stacking of this type of flat conjugated peryleneꢀbased
assemblies. Theoretical calculations predict that the antiparallel πꢀstacking interaction is the most
stable conformation in four tested model naphthalene/peryleneꢀbased dimers. The potential of these
novel semiconductors has been investigated by using them as active layer in bottomꢀgate topꢀcontact
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ꢀ4
OTFTs. All of them show nꢀtype mobilities with the highest value of 1.5×10 for the peryleneimideꢀ
thiophene assembly PITa. This novel building block provides a playground to prepare a plethora of
new materials with different architectures and side chains for electronic applications where nꢀtype
materials with enhanced absorption crossꢀsection are needed.
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Experimental Section
General Methods and materials
All reactions with air sensitive materials were carried out under Ar using standard Schlenk techniques.
TLC was performed using preꢀcoated silica gel 60 F254 and developed in the solvent system indicated.
Compounds were visualized by use of UV light (λ = 254). 230–400 Mesh silica gel was used for column
chromatography.
Toluene and THF were freshly distilled over sodium/benzophenone under nitrogen before use. NBS,
Pd(PPh ) , Trimethyltin chloride, acenaphthene, triisopropoxyborane, 4ꢀbromoꢀ1,8ꢀnaphthalicanhydride
3
4
1, 2ꢀethylꢀ1ꢀhexylamine, tertꢀButyllithium, K CO , CuI, 3ꢀbromothiophene and CsF were purchased
2
3
from commercial suppliers and used without further purification.
5
0
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84
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62
Dione NIDa, 5ꢀbromoacenaphthene, thiopheneꢀ3,4ꢀdiamine, naphthalimide 2a, imide 2b and
8
6
[2,2':5',2''ꢀTerthiophene]ꢀ3',4'ꢀdiamine were prepared according to literature methods.
1
13
H NMR and C NMR spectra were recorded on a 300 and 500 MHz spectrometer. Chemical shifts are
reported in ppm and referenced to the residual nonꢀdeuterated solvent frequencies (CDCl : δ 7.26 ppm
3
1
13
for H, δ 77.0 ppm for C. Mass spectra were recorded by means of MALDIꢀTOF or FAB/IE
techniques. Melting points were collected either in a microscope coupled with a heating plate or using a
capillary melting point apparatus and are uncorrected. UV/Vis absorption spectra were recorded in 1 cm
−
1
cuvettes. Infrared spectra are reported in wavenumbers (cm ). Solids were analyzed on a diamond plate
(ATR) or as films on sodium chloride. Cyclic voltammetry experiments were performed with a
computer controlled potentiostat in a three electrode singleꢀcompartment cell (5 mL). The platinum
2
working electrode consisted of a platinum wire with a surface of A = 0.785 mm , which was polished
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down to 0.5 ꢀm with polishing paste prior to use in order to obtain reproducible surfaces. The counter
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electrode consisted of a platinum wire and the reference electrode was a Ag/AgCl secondary electrode.
An electrolyte solution of 0.1 M TBAPF in freshly distilled and degassed acetonitrile (HPLC) was used
6
in all experiments.
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All calculations were performed using the program GAUSSIAN 09 Rev. B.01. In all cases the
functional B3LYP and a 6ꢀ31G** (6ꢀ31++G** for anions) basis were used following an unrestricted
DFT method for the cation and anion radicals. For geometry optimizations an additional frequency
calculation was performed showing no imaginary frequencies confirming the potential energy minimum
nature of the geometry. Default options for energy minima search and integral accuracy were applied.
8
5
4
-Bromo-N-(2-ethylhexyl)-1,8-naphthalimide
(2a):
A
suspension
of
4ꢀbromoꢀ1,8ꢀ
naphthalicanhydride 1 (2 g, 7.2 mmol) in 60 mL of EtOH was refluxed. Then, 2ꢀethylꢀ1ꢀhexylamine (2
mL, 12.1 mmol) was added and the mixture was heated for 24 h. The solvent was evaporated and the
product was purified by flash column chromatography (SiO , hexane/dichloromethane 9:1) to give 2.75
2
1
g (98 %) as a yellow solid. M.p. 90ꢀ91ºC. H NMR (300 MHz, CDCl ) δ (ppm) = 8.62 (d, J = 7.3 Hz,
3
1
H), 8.52 (d, J = 8.5 Hz, 1H), 8.37 (dd, J = 7.9, 2.4 Hz, 1H), 8.00 (dd, J = 7.9, 2.4 Hz, 1H), 7.8 –7.74
(m, 1H), 4.19ꢀ4.00 (m, 2H), 1.92 (dt, J = 13.0, 6.6 Hz, 1H), 1.48 – 1.09 (m, 9H), 0.89 (dt, J = 15.5, 7.3
1
3
Hz, 6H). C NMR (75 MHz, CDCl ) δ (ppm) = 164.3, 133.5, 132.4, 131.6, 131.5, 130.9, 130.5, 129.4,
3
ꢀ1
1
28.5, 123.5, 122.6, 44.6, 38.3, 31.1, 29.1, 24.4, 23.5, 14.5, 11.0. FTIR (ATR, CHCl ) ν (cm ) = 2957,
3
ꢀ1
2922, 2859, 1701, 1653, 1581, 1348, 1185 cm.
62
4
-Bromo-N-(2,6-diisopropylphenyl)-1,8-naphthalimide (2b):
A suspension of 4ꢀbromoꢀ1,8ꢀ
naphthalicanhydride 1 (1g, 3.6 mmol) in 10 mL of acetic acid and 1.5 mL (7.2 mmol) of 1,6ꢀ
diisopropylaniline was heated to reflux for 4 days. Then water was added, and the solid was filtered,
washed with water, solved in dichloromethane and dried over MgSO The solvent was removed under
4
.
pressure and the crude was purified by chromatography (SiO , Hexane/dichloromethane, 7:3) to yield
2
1
1
1
.07 g (85%) of 2b as a clear solid. H NMR (300 MHz, CDCl ) δ (ppm) = 8.74 (dd, J = 7.3, 1.2 Hz,
3
H), 8.67 (dd, J = 8.5, 1.2 Hz, 1H), 8.50 (d, J = 7.9 Hz, 1H), 8.10 (d, J = 7.9 Hz, 1H), 7.91 (dd, J = 8.6,
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The Journal of Organic Chemistry
7
.2 Hz, 1H), 7.49 (dd, J = 8.3, 7.2Hz, 1H), 7.35 (d, J = 7.7 Hz,2H), 2.73 (hept, J = 6.8 Hz, 2H), 1.17 (d,
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J = 6.8 Hz, 12 H).
Acenaphthene-5-trimethylstannane (3): A solution of 5ꢀbromoacenaphthene (0.3 g, 1.83 mmol) in 4
t
mL of anhydrous THF was cooled to ꢀ78°C. Then, 2.6 mL (4.4 mmol) of BuLi 1.7 M was very slowly
added, under argon. After two hours, trimethyltin chloride (0.47 g, 2.38 mmol) was added under argon
and the resulting mixture was stirred for 24 hours at room temperature. The solvent was evaporated, the
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mixture dissolved in DCM, washed with water and dried over anhydrous MgSO , to give 0.55 g (95%)
4
1
of 3 as alight brown solid. M.p: 68ꢀ70 ºC. H NMR (300 MHz, CDCl ) δ (ppm) = 7.53 (m, 1H), 7.51 (s,
3
13
1
H), 7.40 (t, J = 7.4 Hz, 1H), 7.22 (d, J = 7.2 Hz, 2H), 3.30 (s, 4H), 0.39 (s, 9H). C NMR (75 MHz,
CDCl ) δ (ppm) = 146.9, 146.8, 145.9, 139.0, 137.1, 136.0, 135.7, 127.7 (2C), 124.20, 122.2, 119.2,
3
ꢀ1
1
19.1, 119.0, 30.2. FTIR (ATR, CHCl ) ν (cm ) = 3031, 2978, 2916, 2839, 1600, 1359, 838, 816, 764.
3
+
MS (EI) m/z: (M 318.09, 18%), 303 (100%), 301 (81%), 299 (39%), 273 (31%), found for C H Sn
15 18
+
.
(M , 318.04). HRMS (EI) m/z: calculated for C H Sn: 318.0425, found: 318.0453
15 18
4
-acenaphthene-5-yl-N-(2-ethylhexyl)-1,8-naphthalimide (5a): a) Suzuki coupling: To a degassed
solution of imide 2a (2.8 g, 7.2 mmol) and acenaphteneꢀ5ꢀboronic acid 4 (1.42 g, 7.2 mmol) in 85 mL of
toluene was added 28 mL of a degassed solution of K CO (2M) and Pd(PPh ) (832 mg, 0.72 mmol)
2
3
3 4
under argon. The mixture was refluxed overnight. Then, the solvent was evaporated, and the mixture
was dissolved in DCM, washed with water and dried over anhydrous MgSO . The product was purified
4
(SiO , hexane/diethyl ether 8:2) to give 2.9 g (87 %) of a yellow solid.; b) Stille coupling: To a
2
degassed solution of imide 2a (0.85 g, 2 mmol) and acenaphteneꢀ5ꢀtrimethyl stannane 3 (0.69 g, 2
mmol) in 7 mL of DMF was added Pd(PPh ) (115 mg, 0.1 mmol), CuI (0.038 g, 0.2 mmol) and CsF
3
4
(0.61 g, 4 mmol) under argon. The mixture was heated at 55ºC overnight. Then, the solvent was
evaporated, the mixture dissolved in DCM, washed with water and dried over anhydrous MgSO . The
4
product was purified (SiO , hexane/diethyl ether 8:2) to give 0.7 g (76%) of a yellow solid. M. p.: 128ꢀ
2
1
1
29ºC. H NMR (300 MHz, CDCl ) δ (ppm) = 8.70 (d, J = 7.5 Hz, 1H), 8.61 (dd, J = 7.2, 0.9 Hz, 1H),
3
7
.94 (dd, J = 8.4, 0.9 Hz, 1H), 7.82–7.74 (m, 1H), 7.54 (dd, J = 8.4, 7.4 Hz, 1H), 7.44 (q, J = 7.1 Hz,
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2
H), 7.37 – 7.27 (m, 2H), 7.10 (m, J = 3.2 Hz, 1H), 4.34 – 4.02 (m, 2H), 3.50 (s, 4H), 2.04 (dd, J = 12.4,
1
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6
.2 Hz, 1H), 1.58 – 1.18 (m, 8H), 0.96 (dt, J = 14.1, 7.2 Hz, 6H). C NMR (75 MHz CDCl ) δ (ppm) =
3
164.7, 164.6, 147.2, 146.4, 145.3, 139.3, 132.98, 131.8, 131.4, 131.2, 130.9, 130.6, 129.8, 129.0, 128.6,
26.7, 123.0, 122.0, 120.7, 119.8, 119.0, 44.2, 38.0, 30.9, 30.6, 30.3, 28.8, 24.2, 23.2, 14.22, 10.8. Anal.
calculated for C H NO : C, 83.26; H, 6.77; N, 3.03. Found: C, 83.56; H, 6.88; N, 3.12. HRMS (EI)
1
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32 31
2
m/z: calculated for C H NO : 461.2349, found: 461.2350.
3
2
31
2
4
-acenaphthene-5-yl-N-(2,6-diisopropylphenyl)-1,8-naphthalimide (5b): To a degassed solution of
imide 2b (0.828 g, 1.9 mmol)and acenaphteneꢀ5ꢀboronic acid (0.376 g, 1.9 mmol) in 25 mL of toluene
was added 9.5 mL of a degassed solution of K CO (2M) and Pd(PPh ) (0.219 mg, 0.19 mmol) under
2
3
3 4
argon. The mixture was refluxed overnight. Then, the solvent was evaporated, and the mixture was
dissolved in DCM, washed with water and dried over anhydrous MgSO . The product was purified
4
1
(SiO , hexane/DCM 8:2) to give 0.9 g (93%) of a yellow solid. M.p.: 318ꢀ320ºC. H NMR (300 MHz,
2
CDCl ) δ (ppm) = 8.77 (d, J = 7.5 Hz, 1H), 8.68 (dd, J = 7.3, 1.2Hz, 1H), 8.03 (dd, J = 8.5, 1.2 Hz, 1H),
3
7.85 (d, J = 7.5 Hz, 1H), 7.62 (dd, J = 8.5, 8.4 Hz, 1H), 7.49 (m, 3H), 7.37 (m, 4H), 7.11 (m, 1H), 3.47
13
(s, 4H), 2.76 (hept, J = 6.8, 2H), 1.13 (m, 12H). C NMR (CDCl , 75 MHz) δ (ppm) = 164.3, 164.2,
3
1
1
1
47.3, 146.4, 145.7, 139.3, 133.4, 131.7, 130.9, 130.6, 129.7, 129.5, 129.1 129.0, 128.6, 126.7, 124.0,
ꢀ1
22.9, 121.9, 120.7, 119.9, 119.0, 53.4, 30.6, 30.3, 29.2, 24.0. FTIR (ATR, CHCl ) ν (cm ): 2964, 1708,
3
+
667, 1588, 1356, 1237, 784. MS (EI) m/z: 510 (M+1, 38%), (M , 509.2, 97%), 492 (25%), 467 (38%),
+
468 (100%), 349 (29%) calculated for C H NO (M , 509.6). HRMS (EI) m/z: calculated for
3
6
31
2
C H NO : 509.2349, found: 509.2348
36
31
2
N-(2-ethylhexyl)-1,2-dihydrocyclopenta[cd]perylene-7,8-dicarboximide (6a): Method a) A mixture
of potassium tertꢀbutoxide (0.7 g,6 mmol) and DBN (0.5 g, 6 mmol) were heated for 1 h to 140 ºC
under argon. Then, imide 5(100 mg, 0.21 mmol) was added in one portion and the mixture was further
heated for 3 h at 140°C. The reaction mixture was cooled to room temperature, and the suspension was
dissolved in DCM, washed with water, and dried over anhydrous MgSO .The crude material was
4
purified (SiO , hexane/diethyl ether 8:2) to give 20mg (20 %) of 6a as a dark red solid. Method b) To a
2
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solution of AlCl (520.5 mg, 3.9 mmol) in 60 mL of anhydrous chlorobenzene the imide 5 (200 mg, 0.43
3
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9
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6
mmol) was added slowly solved in 10 mL of chlorobenzene and the mixture was heated to reflux for 6
hours. Then the crude was cooled to room temperature and water was added. The mixture was extracted
and dried over MgSO and the solvent was evaporated. The red solid was purified by chromatography
4
1
(
SiO dichloromethane) to give 160 mg (80%) of 6a as a red solid. M.p.: 244ꢀ245ºC. H NMR (300
0
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2,
MHz, CDCl ) δ (ppm) = 8.54 (d, 2H, J = 8 Hz), 8.3 (dd, 4H, J = 7.5 Hz), 7.45 (d, 2H, J = 8 Hz), 4.14 (t,
3
2
H), 3.48 (s, 4H), 1.97 (m, 1H), 1.33 (m, 8H), 0.91 (m, 6H). FTIR (ATR, CH Cl ): 2922, 2854, 1684,
2 2
ꢀ1 13
1644, 1582, 1459, 1380, 1353 cm . C NMR (CDCl , 125 MHz) δ (ppm) = 164.3, 149.6, 139.4, 136.9,
3
1
1
30.9, 130.0, 126.9, 125.5, 124.7, 120.9, 119.7, 118.8, 44.2, 38.2, 31.1, 31.0, 29.8, 28.9, 24.3, 23.3,
+
4.3, 10.8. MS (EI) m/z: (M , 459.3, 29%), 347 (71%), 277 (30%), 167 (33%), 149 (43%), 95 (100%),
+
82 (35%) calculated for C H NO (M , 459.2). HRMS (EI) m/z: calculated for C H NO : 459.2193,
32
29
2
32 29
2
found: 459.2192
N-(2,6-diisopropylphenyl)-1,2-dihydrocyclopenta[cd]perylene-7,8-dicarboximide (6b): Method a)
A mixture of potassium tertꢀbutoxide (628 mg, 5.6 mmol) and DBN (462 mg, 3.72 mmol) were heated
for 1 h to 140 ºC under argon. Then, imide 5b (100 mg, 0.19 mmol) was added in one portion and the
mixture was further heated for 3 h at 140°C. The reaction mixture was cooled to room temperature, and
the suspension was dissolved in DCM, washed with water, and dried over anhydrous MgSO . The crude
4
material was purified (SiO , dichloromethane) to give 20 mg (20 %) of a dark red solid. Method b) To a
2
solution of AlCl (460 mg, 3.4 mmol) in 15 mL of anhydrous chlorobenzene the imide 5b (200 mg, 0.38
3
mmol) was added slowly solved in 8 mL of chlorobenzene and the mixture was heated to reflux for 3
hours. Then the crude was cooled to room temperature and water was added. The mixture was extracted
and dried over MgSO and the solvent was evaporated. The red solid was purified by chromatography
4
(
SiO dichloromethane) to give 40 mg (20%) of 6b as a red solid, accompanied of starting material and
2,
1
oligomeric byproducts. M.p: >320 ºC. H NMR (300 MHz, CDCl ) δ (ppm) = 8.63 (d, J = 8.0 Hz, 2H),
3
8
.34 (d, J = 7.6 Hz, 4H), 7.46 (d, J = 7.4 Hz, 1H), 7.34 (d, J = 7.8, 2H), 3.48 (s, 4H), 2.77 (hept, J = 6.8
13
Hz,4H),1.18 (d, J = 6.8 Hz,12H). C NMR (CDCl , 125 MHz) δ (ppm) = 164.1, 149.8, 145.7, 139.9,
3
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37.9, 132.0, 131.3, 129.3, 127.9, 126.0, 125.3, 123.9, 121.3, 121,2, 120.3, 119.2, 31.2, 29.1, 24.0. FTIR
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
ꢀ1
ꢀ1
(ATR, CHCl ) ν (cm ): 2957, 2925, 2855, 1715, 1647, 1459, 1375, 1241, 1181, 1082 cm .MS (EI) m/z:
3
+
+
(M , 507.2, 53%), 464 (18%), 466 (16%), 348 (30%), 347 (100%) calculated for C H NO (M ,
36 29 2
5
07.2). HRMS (EI) m/z: calculated for C H NO : 507.2193, found: 507.2191.
36 29 2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
PIDa: A solution of 160 mg (0.34 mmol) of imide 6a and 407 mg of BSA (1.12 mmol) in 16 mL of
anhydrous chlorobenzene was heated at 130º C overnight. The solution reached an orange color. Then
the mixture was cooled to room temperature and the solvent was removed under vacuo. The red solid
was dissolved in dichloromethane and washed with water. The organic layer was dried with MgSO and
4
the solvent was once again evaporated. The red solid was purified by chromatography (SiO2,
1
dichloromethane/MeOH, 95:5) to give 192 mg (78%) of PIDa as a red solid. M.p: >320 ºC. H NMR
(300 MHz, CDCl ) δ =8.70 (d, 2H, J = 8 Hz), 8.58 (dd, 4H, J = 7.9 Hz, J = 2.2 Hz), 8.17 (d, 2H, J = 7.7
3
Hz), 4.15 (m, 2H), 1.02 (m, 1H), 1.34 (m, 8H), 0.92 (m, 6H). FTIR (ATR, CH Cl ): 3061, 2958, 2926,
2
2
2856, 1730, 1696, 1655, 1608, 1585, 1438, 1413, 1381, 1356, 1316, 1240, 1200, 1173, 1126, 1096,
ꢀ1
1
071, 1019, 851, 826, 788, 746, 687 cm . HRMS (EI) m/z: calculated for C H NO : 487.1778, found:
32 25 4
4
87.1770.
PIDb: A solution of 78 mg (0.15 mmol) of imide 6b and 180 mg of BSA (0.49 mmol) in 8 mL of
anhydrous chlorobenzene was heated at 130º C overnight. The solution reached an orange color. Then
the mixture was cooled to room temperature and the solvent was removed under vacuum. The red solid
was dissolved in dichloromethane and washed with water. The organic layer was dried with MgSO and
4
the solvent was once again evaporated. The red solid was purified by chromatography (SiO2,
1
dichloromethane) to give 79 mg (95%) as a red solid. M.p: >320 ºC. H NMR (300 MHz, CDCl ) δ =
3
8
.76 (d, 2H, J = 8 Hz), 8.63 (dd, 4H, J = 7.9 Hz, J = 2.1 Hz), 8.2 (d, 2H,J = 7.7 Hz), 7.51 (m, 1H), 7.36
13
(d, 2H, J = 7.8 Hz), 2.73 (m, 2H), 1.18 (d, 12H, J = 6.8 Hz). C NMR (CDCl , 175 MHz) δ (ppm) =
3
187.2, 163.6, 145.7, 135.5, 135.1, 133.8, 132.2, 130.8, 129.9, 129.3, 128.7, 126.5, 124.3, 124.2, 123.7,
23.6, 122.9, 96.2, 29.3, 24.1. FTIR (ATR, CH Cl ): 2951, 2926, 2852, 1731, 1704, 1666, 1463, 1176,
1
2
2
ꢀ1
+
1148, 1118, 1103 cm . MS (EI) m/z: (M , 535.19, 31%), 508 (37%), 391 (37%), 361 (37%), 281 (33%),
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+
2
19 (58%), 207 (100%) calculated for C H NO (M , 535.17). HRMS (EI) m/z: calculated for
2
6
25
4
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
C H NO :535.1784, found: 535.1779
36
25
4
PITa: Under argon atmosphere 3,4ꢀdiamine thiophene, 15 mL of anhydrous chloroform, 40 mg (0.082
mmol) of PIDa and a catalytic amount ofpꢀTSA were heated to 50 ºC and left stirring overnight. Then,
the crude was washed with NaHCO and water. The organic layer was dried over MgSO and the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
4
solvent was removed under pressure. The mixture was solved in dichloromethane and precipitated and
13
washed with MeOH to yield 24 mg (52%) of a dark solid. M.p: >200 ºC. C NMR could not be
1
performed due to precipitation of the sample in all solvents. H NMR (300 MHz, CDCl ) δ (ppm) = 8.59
3
(bs, 2H), 8.48 (bs, 4H), 8.25 (bs, 2H), 7.96 (s, 2H), 4.15 (m, 2H), 1.97 (m, 1H), 1.42 (m, 8H), 0.91 (m,
6
H). FTIR (ATR, CH Cl ): 2958, 2924, 2854, 1737, 1694, 1653, 1584, 1516, 1459, 1413, 1380, 1353,
2
2
ꢀ1
1316, 1260, 1170, 1095, 1060, 1020, 802, 752, 693, 607, 568.cm . HRMS (EI) m/z: calculated for
C H N O S: 565.1818, found: 565.1817.
36
27
3
2
PITb: Under argon atmosphere 3,4ꢀdiamine thiophene, 7 mL of anhydrous chloroform, 20 mg (0.039
mmol) of the dione PIDb and a catalytic amount of pꢀTSA were heated to 50 ºC and left stirring
overnight. Then the crude was washed with NaHCO and water. The organic layer was dried over
3
MgSO and the solvent was removed under pressure. The mixed was solved in dichloromethane and
4
1
precipitated and washed with MeOH to yield 91% (21 mg) of a dark red solid. M.p: >200 ºC. H NMR
(
300 MHz, CDCl ) δ = 8.70 (bs, 2H), 8.56 (bs, 4H), 8.29 (bs, 2H), 7.97 (s, 2H), 7.50 (m, 1H), 7.37 (d,
3
2
2
8
H, J = 7.3 Hz), 2.79 (m, 2H), 2.02 (m, 1H), 1.20 (d, 12H, J = 6.7 Hz). FTIR (ATR, CH Cl ): 2960,
2 2
925, 2866, 1704, 1665, 1584, 1516, 1549, 1412, 1359, 1321, 1246, 1194, 1175, 1141, 1092, 1050, 846,
ꢀ1 13
18, 752, 717, 694, 607, 568 cm . C NMR (175 MHz, CDCl ) δ (ppm) = 163.8, 145.8, 139.4, 136.0,
3
132.2, 129.7, 124.9, 124.2, 122.6, 122.0, 118.6, 114.2, 96.2, 29.8, 24.1. HRMS (EI) m/z: calculated: for
C H N O S: 613.1818, found: 613.1813.
40
27
3
2
PITT: Under argon atmosphere [2,2':5',2''ꢀTerthiophene]ꢀ3',4'ꢀdiamine (27.2 mg, 0.097 mmol), 7 mL of
anhydrous chloroform, 30 mg (0.061mmol) of dione PIDa and a catalytic amount of pꢀTSA were heated
to 50 ºC and left stirring overnight. Then the solvent was evaporated and the dark solid was washed with
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cold and hot methanol to yield 63 % (27.9 mg) of a dark blue solid. M.p: >200 ºC. H NMR (500 MHz,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
C D Cl , 60 ºC) δ = 7.94 (bs, 2H), 7.88 (bs, 2H), 7.84 (bs, 2H), 7.67 (bs, 2H), 7.32 (s, 2H), 7.07 (s, 2H),
2
2
4
6.84 (s, 2H), 3.49 (m, 2H), 1.97 (bs, 1H), 0.28 (m, 6H). There is a signal at 6.54 ppm that disappears
when drops of TFA are added, indicating that this signal may be due to aggregation. FTIR (ATR,
CH Cl ): 3069, 2953, 2924, 2858, 1694, 1654, 1581, 1413, 1353, 1319, 1240, 1169, 1134, 1094, 1062,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
2
ꢀ1
8
41, 813, 751, 725, 699, 643, 607 cm . HRMS (MALDIꢀTOF) m/z: calculated: for C H N O S
44 32 3 2 3
+
[
M+H]+: 730.1651, found: 730.1599 (M+H ).
NIb: To a solution of 800 mg (3.56 mmol) of acenaphtheneanhidryde in 160 mL of acetic acid was
added dropwise 1.60 mL (7.25 mmol) of the amine and left 4 days under reflux. Then water was
added until a precipitate appeared. The solid was filtered and throroughly washed with water until the
1
pH turned neutral to obtain 1.25 g (91%) of a clear brown solid. M.p. (dec.): 310 ºC. H NMR (300
MHz, CDCl ) δ (ppm) = 8.57 (d, 2H, J = 7.4 Hz), 7.62(d, 2H, J = 7.3 Hz), 7.46 (m, 1H), 7.32 (d, 2H,
3
1
3
J = 7.7 Hz), 3.62 (s, 4H), 2.74 (m, 2H), 1.15 (d, 12H, J = 6.8 Hz). C NMR (75 MHz, CDCl ) δ
3
(ppm) =164.5, 154.3, 146.0, 138.1, 133.4, 131.6, 129.1, 127.3, 124.0, 121.1, 119.4, 31.9, 29.2, 24.1.
ꢀ1
FTIR (KBr) ν (cm ) =3051, 2961, 2925, 2867, 1697, 1659, 1621, 1503, 1456, 1408, 1384, 1362,
1336, 1265, 1234, 1169, 1140, 1096, 1058, 965, 939, 870, 828, 798, 770, 730, 699, 604. HRMS (EI)
m/z: calculated for C H NO : 383.1885, found: 383.1880.
2
6
25
2
NIDb: Over a solution of 730 mg (1.9 mmol) of imide NIb in chlorobenzene, benzeneseleninic acid
anhydride (BSA) (2.2 g, 4.3 mmol) was added. The mixture was heated at 130ºC for 48 hours. Then
the solvent was removed, the solid was dissolved in dichloromethane and washed with water twice.
The organic layer was dried with magnesium sulfate and the solvent was removed by rotary
evaporation. The solid was purified by column chromatography (silica gel flash, dichloromethane) to
1
yield 381 mg (50 %) of NIDb as a yellow solid. M.p (dec.): 265ºC. H NMR (300 MHz, CDCl ) δ
3
(ppm) = 8.88 (d, 2H, J = 7.3 Hz), 8.40 (d, 2H, J = 7.3 Hz), 7.53 (m, 1H), 7.36 (d, 2H, J = 7.7 Hz),
1
3
2
1
.71 (m, 2H), 1.16 (d, 12H, J = 6.9 Hz). C NMR (75 MHz, CDCl ) δ (ppm) =186.3, 162.8, 145.6,
3
ꢀ1
44.1, 132.8, 132.4, 130.2, 130.1, 127.1, 126.8, 124.4, 123.1, 29.4, 24.1. FTIR (KBr) ν (cm ) =
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960, 2924, 2853, 1751, 1739, 1712, 1676, 1589, 1452, 1362, 1334, 1259, 1233, 1175, 1136, 1117,
052, 971, 864, 845, 821, 801, 751, 721. HRMS (EI) m/z: calculated for C H NO : 411.1465,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
6
21
4
found: 411.1463.
NITb: To a degassed solution of naphthalene aromatic dione NIDb (30 mg, 0.07 mmol) and 9.0 mg
0.08 mmol) of thiopheneꢀ3,4ꢀdiamine in 15 mL of CHCl was added a catalytic amount of pꢀTSA.
(
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
The mixture was refluxed overnight under argon. Then, the crude was washed with NaHCO , water
3
and dried over anhydrous MgSO , to give, after chromatography (SiO / dichloromethane/AcOEt
4
2
1
(95:0.5)), 15 mg (43%) of a yellow solid. M.p (dec.): 195 ºC. H NMR (300 MHz, CDCl ) δ (ppm) =
3
8
.77 (d, 2H, J = 7.4 Hz), 8.45(d, 2H, J = 7.4 Hz), 8.12 (s, 2H), 7.52 (m, 2H), 7.43 (d, 2H, J = 7.7 Hz),
13
2
.78 (m, 2H), 1.18 (d, 12 H, J=6.9 Hz). C NMR (75 MHz, CDCl ) δ (ppm) =163.6, 155.7, 154.0,
3
145.9, 141.8, 137.2, 136.1, 133.4, 131.1, 130.8, 130.2, 129.8, 129.5, 124.2, 124.1, 121.9, 119.9, 29.3,
ꢀ1
2
4.1. FTIR (KBr) ν (cm ) = 2963, 2926, 2869, 1800, 1715, 1680, 1645, 1593, 1457, 1383, 1362,
1334, 1235, 1174, 1134, 1100, 1080, 1057, 822, 802, 754. HRMS (EI) m/z: calculated for
C H N O S: 489.1505, found: 489.1507
30
23
3
2
Acknowledgements
This work was financially supported by MINECO (MAT2014ꢀ52305ꢀP and MAT2016ꢀ77608ꢀC3ꢀ2ꢀP)
and the UCMꢀBSCH joint project (GR3/14ꢀ910759). P. E. thanks the URJC for a predoctoral
fellowship. Research at University of Malaga was supported by MINECO (CTQ2015ꢀ66897ꢀP). R. P. O
and I. A.ꢀM. thank MINECO for a “Ramón y Cajal” research contract and for a predoctoral fellowship,
respectively.
Supporting Information
Copies of NMR spectra, spectroscopic, electrochemical and computational details can be found in the
supporting information. This material is available free of charge via the Internet at http://pubs.acs.org.
References
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