Ambipolar pentacyclic diamides with interesting electrochemical and optoelectronic properties

Article abstract of DOI:10.1039/d0cc04629a

Developing organic semiconductors for organic thin film transistors (OTFT) and optoelectronic applications is a challenge. We developed highly crystalline pentacyclic diimides (3) and (4) which showed good OTFT and OLED potential and energy gaps of 2.60 eV and 2.54 eV. They exhibited interesting photo and eletroluminescence activity. Both compounds showed good quantum yields (0.56 for (3) and 0.60 for (4)). This journal is

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Ambipolar Pentacyclic Diamides with Interesting Electrochemical
and Optoelectronic Properties
Received 00th January 20xx,
Accepted 00th January 20xx
Carolina S. Marquesa, Hugo Cruzb, Simon E. Lawrencec, Sandra Gagob, João P. Prates Ramalhoa,d,e
Jorge Morgadof, Luís C. Brancob, Anthony J. Burkea,d*
,
DOI: 10.1039/x0xx00000x
Developing organic semiconductors (OSCs) for organic thin film Both the molecular and bulk structures of the OSC are
transistors (OTFT) and optoelectronic applications is a challenge. important. In the case of the molecular structure, -conjugation
π
We developed highly crystalline pentacyclic diamides (3) and (4) is an essential prerequisite for a molecule to exhibit such
which showed good OTFT and OLED potential and energy gaps of properties. A number of different kinds of molecular systems
2.60 eV and 2.54 eV. They exhibited interesting photo and have been known for some time with this characteristic. These
eletroluminescence activity. Both compounds showed good include rubrene, triphenylene, hexabenzocoronene, 5,11-
quantum yields (0.56 for (3) and 0.6 for (4)).
diphenyltetracene (PPT), phthalocyanine, 4,4’-bis(N-m-tolyl-N-
phenylamino)biphenyl (TPD), (PTCDA) – a perylene diimide –
and perylenetetra carboxyldiimide (PTCDI),4 including dioctyl–
perylene tetracarboxylic diimide (PTCDI–C8H17)2a, which is used
in n-channel transistors. In the case of bulk structure,
supramolecular structure is crucial. The type of crystal packing
and intermolecular arrangement is important. Crystalline OSCs
show regular and tight packing between neighboring molecules
with relatively weak non-covalent bonds, such as hydrogen
bonds, van der Waals forces, charge transfer interactions,
intermolecular orbital overlap, etc.4b The potential of the OSC
for OTFT is assessed by determining their charge carrier
mobility. Some of the best results were obtained in single
crystals. Rubrene was reported by Rogers’s group to have an
intrinsic hole mobility of 15.4 cm²/Vs.5 2,6-di-(2-
naphthyl)anthracene, was shown by Hu’s group2 to have a
charge carrier mobility value of 12.3 cm²/Vs (including a
quantum yield of 29.2% which will be important in the
The development of novel and more efficient (opto)electronic
devices has become the center of much focus in both chemistry
and materials science, due to the profound effect they have on
our lives. In this context, there has been an increased focus on
novel organic and flexible electronics.1 In general, organic
semiconductors, when compared to traditional Si and GaAs-
based technologies, offer unique features such as tunable
electronic structure and physicochemical properties via core
functionalization, mechanical flexibility as well as variable
optical band gaps and ability to be solution processed on a large
scale with low cost.1,2 The introduction of some deformability in
the organic semiconductor is a relevant goal that permits for
example the fabrication of flexible and printed electronic
materials.1,2 Critical to this goal is the development of more
efficient organic semiconductors (OSCs) integrating excellent
charge transport with efficient light emission properties.2.
Organic thin film transistors (OTFTs) are particularly important,
and the number of publications in this field has exploded since
the seminal report by Koezuka in 1987.3
discussion
below).
2,7-dioctyl[1]benzothieno[3,2b]
benzothiophene (C8-BTBT) was shown by Hasegawa’s group to
have a value of 16.4 cm²/Vs (saturation regime) attaining a
highest value of 31.3 cm²/Vs6. Indenone-fused N-heteroacenes7
were shown by Lino’s group to give a value of 12.3 cm²/Vs. In
the case of imide (and analogue) type OSC the values are less
remarkable. Frisbie and coworkers reported a value of 0.1
cm2/Vs (in a thin-film configuration).8 More recently, Felter’s
group reported a best value of 0.32 cm2/Vs for the perylene
diimide (PDI), known as PDI-octyl (which forms large crystalline
aggregates) in a thin-film using pulse radiolysis time-resolved
microwave conductivity (TRMC).9
Important also is the ambipolar charge transport characteristics
of these materials4b. In this case, both the electron (µe) and hole
(µh) mobilities are significant. The best compounds usually have
a small HOMO-LUMO energy gap.10 High values for both µe and
µh in the range 3 to 9 cm²/Vs have been reported for a plethora
a. LAQV-REQUIMTE -University of Évora, Rua Romão Ramalho, 59, 7000-671 Évora,
Portugal
b. LAQV-REQUIMTE -Faculdade de Ciꢀncias e Tecnologia, Universidade Nova de
Lisboa, 2829- 516 Caparica, Portugal
c. School of Chemistry, Analytical and Biological Chemistry Research Facility, Solid
State Pharmaceutical Centre, University College Cork, Cork, Ireland
d. Departamento de Química, School of Science and Technology, University of Évora,
Institute for Research and Advanced Studies, Rua Romão Ramalho, 59, 7000-671
Évora, Portugal
e. Laboratório Hercules, University of Évora, Palácio do Vimioso, Largo Marquês de
Marialva 8, 7000-809 Évora, Portugal
f. Instituto de Telecomunicações and Department of Bioengineering, Instituto
Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, P-1049-001
Lisboa, Portugal
* ajb@dquim.uevora.pt
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/x0xx00000x
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of OSCs4b. Unfortunately, there are few reports on the containing the electrolyte tetrabutylammoniumViepweArrctihcleloOrnalitnee
determination of these parameters for imide (and analogue) (TBAP; 0.1 M) under nitrogen flowDO(I:F1i0g.u10re39s/D0CC04629A
and
type OSCs. Iyer and coworkers reported a µe = 0.6 cm²/Vs for an respectively). Compound ( ) and the unsubstituted parent
1
2
3
imide-type OSC (thin films).11 An amide functionalized compound (4) both presented one chemically irreversible two
coronene, although not a true imide, was shown by De et al. to electron oxidation wave with an anodic peak potential (Epa) at
possess high electron and hole mobilities, µe = 3.59 cm²/Vs and 1.30 V and 1.27 V respectively. Both compounds also presented
µh = 8.84 cm²/Vs.10
two reversible/quasi reversible one-electron transfer reduction
In this communication we report on a new family of condensed waves (Epc1) at −1.45 and -1.52 V and Epc2 at -1.73 and -1.83 V
imide type compounds with interesting OTFT potential and (vs SCE), respectively. In the cathodic direct scan, at different
confirmed electroluminescence properties.
scan rates, two successive reversible/quasi-reversible one
For some time, the Burke group has been interested in efficient electron transfer process, with a formal potential of -1.40 V and
catalytic routes to certain heterocyclic ring systems.12 In an -1.44 V and -1.69 V and -1.77 V (vs. SCE) were observed,
attempt to reduce the number of synthetic steps leading to a respectively. Semiconductors are usually characterized by
key dihydroisoquinolinone target (see Scheme s1, supporting having energy gaps (HOMO-LUMO separation) below 3.0 eV.
information), we inadvertently synthesized the novel chiral The LUMO energies of (
3) and (4) were estimated to be around
fluorescent pentacyclic diamide ( ) which, in the solid state, -3.29 eV and -3.28 eV, respectively (for comparison,
3
exists as a fluorescent crystalline yellow solid (Scheme 1, its naphthalene bis-imide ambipolar field effect transistors, like
crystallinity was confirmed by SEM analysis Fig. s.12(a)). This TPA-PMPI14 presented a value of -2.27 eV). The HOMOs have
compound crystallinity was characterized by X-ray energies of -5.89 eV and -5.82 eV, respectively, determined also
crystallography (Fig. s13), which revealed that the compound from the CV data by using ferrocene as reference to calculate
was slightly twisted, and not completely flat (see Supporting the energy (EHomo= -e[Eoxonset+4.4]) and LUMO (ELumo= -
Information for details). Compound (3
) crystal structure, as e[Eredonset+4.4]).15 (The literature determined value for TPA-
shown in Fig. s8, is characterized by several C-H--O bonding PMPI14 was -5.35 eV). The corresponding electrochemical
interactions which compelled the molecules to form compact energy gaps (EgEC) were estimated to be 2.6 eV and 2.54 eV
layers. A putative mechanism for the synthesis of (
in Scheme s.3 (Supporting Information). Considering the unique DFT) suggesting indeed that these compounds have
structural features of this molecule (significant conjugation, semiconductor properties. The agreement of the
quasi-flatness and pseudo-aromaticity) we immediately electrochemical calculated HOMO energies and the DFT
3) is shown respectively (compared with 3.22 and 3.20 eV calculated by
“
”
envisioned this class of molecule should possess potential calculated values is very good, while for the LUMO energies the
optoelectronic properties, particularly since phthalimide10,11 difference is ≈ 0.6 eV. It is known that the HOMO values can be
based fluorescent probes are well-known and, thus, embarked estimated by cyclic voltammetry with better accuracy when
on several studies to test this hypothesis. The spectroscopic, compared with the LUMO values.16 It was even suggested the
cyclic voltammetry and computational analyses are discussed in use of electrochemical techniques for determining only the
detail below. We also synthesized via a novel synthetic pathway HOMO level and to estimate the LUMO by adding the
that involved a crucial McMurry coupling step (Scheme s2 SI) experimental optical gap value.17 When we calculate the LUMO
the already reported compound
compound was never isolated nor previously characterized)13, calculated values improved remarkably (see Table
without the methoxyl-substituted group, to compare the results direct anodic scan, a chemical irreversible two-electron
with those of compound ( ). The more crystalline nature of ( oxidation wave at 1.30 V and 1.27 V suggests that this is an
(
4
)
(unfortunately this energies in this way the agreement with the theoretical
1
). In the
3
3)
may be due to the presence of stereocenter and the OCH3 group irreversible oxidation process. Coulometry experiments were
(see SEM analysis in Fig. s.12). Density-functional theory (DFT) conducted but it was not possible to isolate any product (see
and time-dependent density-functional theory (TD-DFT) supporting information). These results may indicate limitations
calculations were carried out to investigate geometrical, optical for hole transport for amorphous/disordered films.
and electronic properties of compounds (
3
) and (4) (SI).
Table 1 The Suite of Electrochemical Parameters Measured for Compounds (3) and
(4)
a Calculated by adding the optical band gap and CV HOMO level.
.
MeO
HOMO (eV)
LUMO (eV)
Compound
Epc1
E0
Epc2
E0
Epa3
O
CV DFT
CV
DFT
CV+Opta
O
O
Deprotection
OMe
OMe
N
N
Good optoelectronic
properties
N
H
-1.45
-1.40
-1.73
-1.69
1.30 -5.89 -5.95 -3.29 -2.73 -2.87
Intramolecular
Cyclization
X
(1)
(3)
X= I, Br, Cl
-1.52
-1.44
-1.83
-1.77
1.27 -5.82 -5.89 -3.28 -2.68
-2.80
Scheme 1. Serendipitous synthetic approach to the fluorescent pentacyclic
diamide ( ).
3
All spectroelectrochemical studies using UV-Vis-NIR
spectroscopy of (3) and (4) were studied and recorded in MeCN
with the same electrolyte (TBAP; 0.1 M) under nitrogen flow. As
shown in Figure 2, the initial spectrum of (3) (note: the
Standard electrochemical properties were studied by cyclic
voltammetry (CV) and the spectroelectrochemical UV−Vis-NIR
spectra of (3) were studied and recorded in acetonitrile (MeCN)
2 | J. Name., 2012, 00, 1-3
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spectrum of (4) is not shown) is composed of two major transitions, and is in line with the experimentalVoiebwsAertricvleaOtinolinne,
DOI: 10.1039/D0CC04629A
absorption bands: a narrower band with a maximum at 280 nm showing a depletion of electronic charge on the oxygen and
and a broader band between 325 and 450 nm.
nitrogen atoms. The pattern is similar for both compounds and
the OCH3 group in (3) does not seem to significantly change the
electronic distribution.
1.5x10-4
1.0
2.0x10-4
1.0
oxred 20mV/s
oxred 50mV/s
oxred 100mV/s
oxred 200mV/s
B)
A)
redox 20mV/s
redox 50mV/s
redox 200mV/s
Figure 3: Normalized absorption (A) and emission (B) spectra (

exc=390 nm) of (3)
0.5
in different solvents.
0.0
0.0
-0.5
-1.0
1
1
-2.0
-1.0
0.0
1.0
-2.0
-1.0
0.0
1.0
toluene
Potential (V vs. SCE)
toluene
Potential (V vs. SCE)
chloroform
acetonitrile
ethanol
chloroform
acetonitrile
ethanol
Figure 1: Cyclic voltammetry studies of (3) as a 1 mM solution in MeCN with 0.1 M
TBAP in a 3-electrode configuration cell using WE as a glassy carbon, CE platinum
wire and SCE as the reference electrode, at different scan rates from 20–750 mV
s-1. Electrochemical window A) 0/1.5/-2/0 and B) 0/-2/1.5/0.
0
250
0
400
350
450
550
650
500
600
700
Wavelength (nm)
Wavelength (nm)
Following the results of the cyclic voltammetry study, it was
realized that there was the potential for the generation of a
fluorescent and electrochromic radical anion and, therefore, a
charge of -1.5 V (vs. SCE) was applied for 3600 s. 15s after
commencing the experiment, the spectra changed, with a
notable decrease in intensity in the broad band (between 325-
450 nm) and two new absorption bands appearing at 480 and
620 nm, respectively. There was a bathochromic shift of the
band at 250 nm to 280 nm. Such observations can be
interpreted as the disappearance of the neutral compound and
Figure 4: Contour plots of the electron density difference (Δρ) upon the lowest
energy excitation S0->S1 of the neutral compounds (3) (on the left) and (4) (on the
right) in acetonitrile solution. Magenta and blue isosurfaces represent negative
(loss of electrons) and positive (electron gain) values, respectively.
the emergence of
a negatively charged species. This
interpretation is corroborated by the TD-DFT calculation that
assign the decreasing band between 325-450 nm to the neutral
compound and the emerging bands at 480 and 620 nm to the
negatively charged species (Table s3, Fig s10) The intensity of
the absorption bands at 480 and 620 nm increase until reaching
3000s. The oxidation process of (3) was also studied (Scheme
s.4).
Figure 3B shows the normalized emission spectra in the same
solvents (exc = 390 nm) with a maximum around 465 nm (Table
s.3). Compound (3) exhibits a bright blue luminescence with a
high quantum yield of 0.56 that was determined by the
comparative method using 7-(diethylamino)-4-methylcoumarin
(Coumarin 1) (Ф 4)
= 0.5) in ethanol as reference.19 Compound (
possessed a comparable behavior to (
0.60.
3) with a quantum yield of
1.0
refrerence_initial
Eapp=-1.5V
Eapp
Eapp
Eapp
Eapp
Eapp
Eapp
Eapp
Eapp
=
=
=
=
=
=
=
=
-
-
-
-
-
-
-
-
1.5V after 15s
1.5V after 210s
1.5V after 600s
1.5V after 1200s
1.5V after 1800s
1.5V after 2100s
1.5V after 3000s
1.5V after 3600s
0.8
0.6
0.4
0.2
0.0
The electroluminescence properties of compound (3) were assessed
in a simple organic light-emitting diode (OLED) structure, where the
active layer was made of neat compound (3) deposited by spin-
coating, which showed acceptable performance. In particular, a
maximum luminance of 44 cd/m2 was achieved with a luminous
efficiency of 0.04cd/A, a result that can be optimized (See the SI for
details of the device preparation and performance). The stability of
these compounds in films still required further optimization (see SI).
Aging of the thin films leads to bleaching under environmental
conditions. Thin films of these compounds tend to crystallize over
time, a process that is slower for compound (3), which we attribute
to the presence of the methoxyl group.
200
300
400
500
CDO (nm)
Wavelength (nm)
600
700
800
Figure 2: Spectroelectrochemical experiments of (3) 1 mM solution in MeCN with
the electrolyte TBAP (0.1 M) in a 3-electrode configuration cell, WE platinum grid,
CE platinum wire, reference electrode Ag/AgCl. Applied Potential -1.5 V and the
spectrum measured over the following period: 15, 210, 600, 900, 1200, 1800,
2100, 2700, 3000 and 3600 s.
The normalized absorption spectra for (3) in toluene,
chloroform, acetonitrile and ethanol are shown in Figure 3 A))
and contain three main absorption bands: around 280, 390 and
410 nm. These bands are in good agreement with the TD-DFT
calculation results, where the lower energy vertical transitions
at 401 nm and 403 nm (mainly of HOMO->LUMO character)
were calculated for compounds (3) and (4), respectively (Figure
s.19 and Tables s.9 and s.14). A slight hypsochromic shift is
observed as the polarity of the solvent increases which is
consistent with n→* electronic transitions.18 The calculated
electronic density rearrangement that occurs upon the S0->S1
transitions is depicted in Figure 4. It represents the difference
between the electronic densities of the states involved in the
In order to gain further insights into the applicability of these
compounds as OSC in OTFTs we used Marcus theory20and
conducted a number of key calculations to determine their
reorganization energies (
detailed discussion) and to estimate the mobility of compound
), for which we have an X-ray crystal structure data available
(unfortunately, we did not have an X-ray crystal structure for
λ, see Supporting Information for a
(
3
(
4
)) . Reorganization energy is a metric affording insight into
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electron and hole mobility in OSC materials.21 and accounts for project UIDB/50008/2020 for financial support. We thank
View Article Online
DOI: 10.1039/D0CC04629A
the energetic cost of the geometry adjustment on the Declan Gilheany (University College Dublin) and John Hartwig
hole/electron transport process. The lower the
energy cost of the geometry relaxations and the higher the synthesis of compound (3)
electron transfer rate.21 DFT calculations of
for OSC materials
are rare. In our studies we calculated h to be 0.453 eV and λ e
to be 0.380 eV for (3) and 0.421 and 0.364 eV for (4). Since for
both compounds h and λ e have almost similar values we can
anticipate that the compounds are likely to show ambipolar
behavior. However, since the e values are slightly smaller it can
λ the smaller the (University of Berkley) for discussions on the mechanism for the
.
λ
λ
Conflicts of interest
There are no conflicts to declare.
λ
λ
be assumed that the compounds will have a leaning towards n-
type. The calculated electron carrier mobility µ– and the hole
Notes and references
1
2
(a) K. Feron, R. Lim, C. Sherwood, A. Keynes, A. Brichta, P. C.
Dastoor, Int. J. Mol. Sci. 2018, 19, 2382. (b) C. Wang, H.
Dong, L. Jiang, W. Hu, Chem. Soc. Rev. 2018, 47, 422. (c) V.
Coropceanu, J. Cornil, D. A. da S. Filho, Y. Olivier, R. Silbey, J.-
L. Brédas, Chem. Rev. 2007, 107, 926. (d) J. D. Myers, J. Xue,
Polymer Reviews 2012, 52, 1.
carrier mobility µ+ for compound (
cm2V-1s-1, respectively showing the compound are likely to show
ambipolar behavior with leaning towards n-type
3) were 0.731 and 0.379
a
semiconductor (corroborating the results obtained for the
reorganization energies above)(see the SI). Moreover,
For key publications see: (a) H. Klauk, Chem. Soc. Rev. 2010
,
comparing the results for (3) and (4), the lower
λ values of (4)
43, 2643. (b) J. Li, K. Zhou, J. Liu, Y. Zhen, L. Liu, J. Zhang, H.
suggest that it should have better mobility than (3). This could
be due to the presence of the stereogenic center in (3) and an
electron-donating methoxyl group.
Dong, X. Zhang, L. Jiang, W. Hu, J. Am. Chem. Soc. 2017, 139,
17261.
H. Koezuka, A. Tsumura, T. Ando, Synth. Metals 1987, 18,
699.
(a) V. Coropceanu, J. Cornil, D. A. da S. Filho, Y. Olivier, R.
Silbey, J.-L. Brédas, Chem. Rev. 2007, 107, 926 and
references cited therein. (b) Y. Wang, L. Sun, C. Wang, F.
Yang, X. Ren, X. Zhang, H. Dong, W. Hu, Chem. Soc. Rev.
2019, 48, 1492.
V. C. Sundar, J. Zaumseil, V. Podzorov, E. Menard, R. L.
Willett, T. Someya, M. E. Gershenson, J. A. Rogers, Science
2004, 303, 1644.
H. Minemawari, T. Yamada, H. Matsui, J. Y. Tsutsumi, S. Haas,
R. Chiba, R. Kumai, T. Hasegawa, Nature, 2011, 475, 364.
F. Ding, D. Xia, C. Ge, Z. Kang, Y. Yang, R. Fan, K. Lin, X. Gao, J.
Mater. Chem. C, 2019, 7, 14314.
R. J. Chesterfield, J. C. McKeen, C. R. Newman, C. D. Frisbie,
P. C. Ewbank, K. R. Mann, L. L. Mille, J. App. Phy. 2004, 95,
6396.
3
4
In conclusion, we have synthesized two novel lightweight
pentacyclic imide compounds (3) and (4) with interesting
optoelectronic and electrochemical properties. Both
compounds showed very good electrochemical properties with
energy gaps of 2.60 eV and 2.54 eV, respectively, indicating that
they are suitable OSC compounds. Compound (3) showed very
interesting fluorescence properties, with two new absorption
bands at 480 and 620nm appearing upon its reduction. Both
compounds showed reasonable fluorescence efficiency in
solution. The preliminary tests on OLEDs based on compound
(3) suggest these are interesting compounds for optolectronic
applications. Reorganization energy and carrier mobility
calculations confirmed the suitability of both compounds as
5
6
7
8
9
K. M. Felter, V. M. Caselli, D. D. Gꢃnbaꢄ, T. J. Savenije, F. C.
Gro-zema, ACS Eng. Mat. 2019, 2, 8010.
OSC active components (
λ
h = 0.453 eV and
λ
λ
e = 0.380 eV and µ–
h = 0.421 and λ e
= 0.731 and µ+ = 0.379 cm2V-1s-1 for (3) and
=
10 J. De, I. Bala, S. P. Gupta, U. K. Pandey, S. K. Pal, J. Am. Chem.
Soc. 2019, 141, 18799.
0.364 eV for (4), with a slight predominance for n-type
semiconductor behavior. Work is on-going on the synthesis of
further derivatives with potentially superior optoelectronic
properties, charge mobilities and on improving their stability.
11 A. Kalita, N. V. V. Subbarao, I. Iyer, J. Phys. Chem. C, 2015
,
119, 12772.
12 For some examples see: (a) C. S. Marques, D. Peixoto, A. J.
Burke, RSC Adv. 2015, 5, 20108. (b) C. S. Marques, A. J.
Burke, Eur. J. Org. Chem. 2016, 806.
13 S. Mann, L. Eveleigh, O. Lequin, O. Ploux, Anal. Biochem.
2013, 432, 90.
Acknowledgements
14 S.-H. Hsiao, Y.-Z. P. Chen, Dyes Pigment. 2017, 144, 173.
15 P. Gawrys, D. Boudinet, A. Kornet, D. Djurado, S. Pouget, J.-
M. Verilhac, M. Zagorska, A. Pron, J. Mater. Chem., 2010, 20,
1913.
We are grateful to Fundaꢀꢁo para a Ciꢂncia e a Tecnologia (FCT)
for generous finance to the University of Évora team through
strategic project Pest-OE/QUI/UI0619/2019. Part of this work
was supported by the Associate Laboratory for Green
Chemistry-LAQV which is financed by national funds from
FCT/MCTES (UID/QUI/50006/2019), project “SunStorage-
Harvesting and storage of solar energy”, with reference POCI-
01-0145-FEDER-016387 and by national funds (project GlyGold,
PTDC/CTM-CTM/31983/2017), through CT–FCT. H. Cruz and L.
C. Branco thank to FCT, MCTES, for norma transitória DL
57/2016 Program Contract and IF/0041/2013/CP1161/CT00,
respectively. S. E. Lawrence thanks University College Cork 2013
Research Fund and Science Foundation Ireland under grant
05/PICA/B802/EC07. J. Morgado thanks FCT/MCTES under the
16 P. Acevedo-Peña, A. Baray-Calderón, H. Hu, I. González, V.
Ugalde-Saldivar, J. Sol. State Electrochem., 2017, 21, 2407.
17 J. Carlé, M. Helgesen, N. Zawacka, M. Madsen, E. Bundgaard,
F. Krebs, J. Pol. Sci. Part B: Pol. Phys., 2014, 52, 893.
18 K. K. Rohatgi-Mukherjee, Fundamentals of Photochemistry,
Wiley Eastern Limited: Calcutta, 1978
.
19 M. Taniguchi, J. S. Lindsey, Photochem. Photobiol. 2018, 94,
290.
20 R. A. Marcus, J. Chem. Phys. 1956, 24, 966.
B. C. Lin, C. P. Cheng, Z. P. M. Lao, J. Phy. Chem. A, 2003, 107,
5241.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC04629A
Ambipolar Pentacyclic Diamides with Excellent Electrochemical and
Optoelectronic Properties
Carolina S. Marquesa, Hugo Cruzb, Simon E. Lawrencec, Sandra Gagob, João P. Prates Ramalhoa,d,e, Jorge
Morgadof, Luís C. Brancob, Anthony J. Burkea,d*
We report on the application of novel small-molecule highly crystalline pentacyclic diamides
possessing significant OTFT and OLED potential.