Visible-light-mediated synthesis of azabenzannulated perylenediimide-based light-harvesting dyads

Article abstract of DOI:10.1021/acs.joc.0c01497

Intramolecular imine photocyclization has been explored for grafting on the bay region of perylenediimide (PDI) different electro- and photoactive chromophores to achieve new AzaBenzannulated-PDI (AzaBPDI) dyads. Triphenylamine (TPA), fluorene (Fl), peryl

Full text of DOI:10.1021/acs.joc.0c01497

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Article
Visible-Light Mediated Synthesis of AzaBenzannulated
Perylenediimide-Based Light Harvesting Dyads
Lou Rocard, Antoine Goujon, Rayane El-Berjawi, Thomas Cauchy, and Piétrick Hudhomme
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01497 • Publication Date (Web): 09 Sep 2020
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Visible-Light Mediated Synthesis of AzaBenzannulated Perylenediimide-Based
Light Harvesting Dyads
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Rayane El-Berjawi, Lou Rocard, Antoine Goujon, Thomas Cauchy, and Piétrick Hudhomme*1
1 Laboratoire MOLTECH-Anjou, UMR CNRS 6200, UNIV Angers, SFR Matrix, 2 Bd
Lavoisier, ANGERS Cedex, 49045 France
*pietrick.hudhomme@univ-angers.fr (Piétrick Hudhomme)
Abstract An intramolecular imine photocyclization has been explored for grafting on the bay
region of perylenediimide (PDI) different electro- and photoactive chromophores to reach new
AzaBenzannulated-PDI (AzaBPDI) dyads. Triphenylamine (TPA), fluorene (Fl), perylenemo-
noimide (PMI) and perylenediimide (PDI) units have been successfully assembled to AzaBPDI
using this straightforward one-pot synthesis starting from the easily accessible 1-aminoPDI. This
original procedure was compared to the well-known Pictet-Spengler reaction and appears to be an
attractive alternative in terms of versatility and efficiency with higher yields obtained. The optical
and electrochemical properties of these molecular systems demonstrated large absorption capabil-
ities in the visible range, good accepting abilities with low-LUMO levels and efficient electronic
interactions between chromophoric units such as energy or electron transfers. In addition, with their
large dihedral angle estimated by theoretical calculations, those dyads should present interesting
applications in various organic optoelectronic devices. In particular, the PMI-AzaBPDI and PDI-
AzaBPDI dyads presenting low-LUMO levels, a broad absorption in the visible range and a twisted
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conformation make them good candidates as Non-Fullerene Acceptors (NFAs) in organic solar
cells (OSCs).
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Introduction
Perylenediimide (PDI) derivatives have emerged as one of the most important classes of dyes and
pigments1 thanks to their outstanding chemical, thermal and photochemical stabilities,2 strong elec-
tron acceptor capabilities and semiconducting behaviour. Because of their absorption properties
and high quantum yield of fluorescence emission, PDI based materials have received much atten-
tion for their utilization in photoinduced electron and/or energy transfer processes to construct
light-harvesting arrays and artificial photosynthetic systems.3 In addition, over the last decade, PDI
derivatives, and in particular three dimensional PDI-based multimers (Figure 1a), have been inten-
sively studied in Organic Solar Cells (OSCs) as a promising class of Non-Fullerene Acceptors
(NFAs).4 The PDI multimerization or decoration can be achieved by means of linkage at the imide,
bay or ortho positions. For reasons of synthetic accessibility, electro- and photoactive counterparts
are usually introduced by condensation of a primary amine onto anhydride functionality, most often
at the imide position and more rarely on its bay region.5 Functionalization at the bay region is
commonly achieved through pallado-catalyzed cross-coupling reaction or nucleophilic substitution
starting from 1-bromoPDI derivative.6 The latter being not easily accessible from a synthetic point
of view, other strategies have recently emerged starting from more largely scalable 1-nitroPDI.7
We have recently demonstrated that 1-nitroPDI could be engaged in Suzuki-Miyaura reaction to
synthesize PDI multimers in good yields, making it an attractive alternative to 1-bromoPDI.8 This
nitrated derivative can also be reduced into 1-aminoPDI by catalytic hydrogenation, opening new
synthetic possibilities (Figure 1b).9 In particular, Z. Wang and co-workers,10 and later the group of
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F. Würthner,11 exploited 1-aminoPDIs to prepare a library of mono and bis-AzaBenzannulated
Perylenediimides (AzaBPDI) via a Pictet-Spengler type reaction, unfortunately in moderate yields.
On the other hand, C. Cheng, Y. Xiao and coll. reported an alternative pathway towards the syn-
thesis of bisazacoronene bisimides involving the oxidative photocyclization of an aliphatic imine
grafted on the bay of perylene tetraester core, an approach that required several subsequent steps
before reaching the desired diimide derivative.12 Very recently, we have reported a straightforward
procedure directly on the diimide scaffold for the synthesis of AzaBPDI and AzaBPDI dimers in
high yields and proved its large scope. This methodology relies on a one-pot three steps sequence
starting from 1) a condensation between 1-aminoPDI and an aldehyde, 2) followed by the visible-
light-promoted photocylization of the corresponding imine and 3) its subsequent oxidative re-aro-
matization by DDQ.13 With the aim of exploiting our procedure, we have been interested in syn-
thesizing original AzaBPDI dyads by attaching electro- and photoactive electron-rich triphenyla-
mine (TPA) or fluorene (Fl) species and electron-poor perylenediimide (PDI) or perylenemo-
noimide (PMI). We present herein the synthesis of those core-extended AzaBPDIs derivatives, in
addition to electronic and photophysical properties of these light-harvesting dyads.
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Figure 1. Structure of a) PDI and b) AzaBPDI, and synthetic strategies for their multimerization.
Results and discussion
The synthesis started from 1-nitroPDI 1 which is prepared nearly quantitatively in multigram scale
without requiring more purification than a simple precipitation.8a In contrast to the preparation of
1-bromoPDI which requires a fastidious purification by column chromatography,14 the introduction
of the nitro electron-withdrawing group on the PDI backbone enables the selective mononitration
over dinitration.15 Catalytic hydrogenation of 1-nitroPDI 1 in the presence of H2 along with Pd/C
catalyst in THF afforded 1-aminoPDI 2.9c The assembly of the dyads was performed by combining
1-aminoPDI 2 with functionalized aldehydes, so-called 4-formyltriphenylamine (TPA-CHO) 3, 2-
fluorene carboxaldehyde (Fl-CHO) 4, 1-(4-formylphenyl)perylenediimide (PDI-CHO) 5 and 9-(4-
formylphenyl)perylenemonoimide (PMI-CHO) 6. Conditions to prepare the imine intermediate re-
quire the use of trifluoroacetic acid in dry solvent (CH2Cl2 or DMF) under argon atmosphere and
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depend on the amount of introduced aldehyde. For the preparation of dyads 7 and 8, the imine
condensation was achieved using 3 equivalents of aldehyde 3 and 4, respectively, in CH2Cl2 at 50
°C for 1-2 h in the presence of a catalytic amount of TFA. The syntheses of dyads 9 and 10 using
1.1 equivalent of precious compounds 5 and 6, respectively, required the heating of the reaction in
DMF at 130 °C overnight with an excess of TFA, and in the presence of activated molecular sieves
(MS) 3Å to trap water formed during the condensation. After dilution in a significant volume of
CH2Cl2, the cyclization was performed under exposure to visible light at room temperature for 1-2
h until complete conversion of the Schiff base into cyclized intermediate. A stoichiometric addition
of DDQ allowed its fast conversion into AzaBPDI based architecture, typically in 5 to 30 min
relying on the solubility of the material. The reaction sequence was particularly easy to follow
when colourless aldehyde 4 was used: the blue solution of amine 2 turned to purple after completion
of the imine formation, progressed to green during the photocyclization, and finally gave a yellow
colour after the re-aromatization (see S.I., Figure S24). Using TPA-CHO 3, prepared according to
literature,16 or commercially available Fl-CHO 4, donor-acceptor systems were obtained in 77%
for AzaBPDI-TPA 7 and 84% for AzaBPDI-Fl 8. For the preparation of dyads 9 and 10, the 4-
formylphenyl moiety was grafted onto PDI8a and PMI17 following methods developed in our group.
The syntheses were then carried out with amine 2 to afford dyads 9 and 10 in 69% and 79% yields,
respectively. The reaction using benzaldehyde to prepare compound 113a was also performed in
83% yield as a reference for further electrochemical and spectroscopic studies. Remarkably, this
original visible-light mediated procedure (Method A) afforded target compounds in significantly
higher yields than the conditions inspired by the Pictet-Spengler reaction (Method B). The latter
were investigated by stirring 1-aminoPDI 2 and the aldehyde derivatives at 130°C in anhydrous
DMF, in the presence of an excess of triflic acid and activated MS 3Å to thermically cyclize the
iminium intermediate. Subsequent oxidation, carried out by treatment with oxygen or DDQ, gave
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dyads 7 (46% yield), 8 (35%), 9 (25%) and 10 (41%) in moderate yields (Scheme 1). All dyads
were characterized by 1H NMR, HRMS and 13C NMR in the case of compound 7 and 8. The low
solubility of 9 and 10 prevented the acquisition of a satisfying 13C spectra, even at high temperature
in deuterated tetrachloroethane. For evaluating their performance as NFA in OSC devices, the cy-
clohexyl chains will be further replaced by swallow-tailed highly solubilizing substituents to ensure
high processability and appropriate film morphology.
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Scheme 1. Synthesis of AzaBPDI-based dyads 7, 8, 9 and 10. For 11, dyads 7 and 8 using Method
A : 1) 3 equiv. of aldehyde, CH2Cl2, 50 °C, 2 h. For dyads 9 and 10: 1) 1.1 equiv. of aldehyde,
DMF, 130 °C, overnight. The yields given in grey within parentheses correspond to those obtained
through the Pictet-Spengler type reaction (Method B : see experimental section).
The optical properties of PDI-based materials were analyzed in CHCl3 solutions by steady-state
UV-Vis absorption and fluorescence spectroscopy and data are depicted in Table 1. PDI 5, PMI 6
and AzaBPDI 11 in CHCl3 solutions were used as references. PDI reference 5 presents the three
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characteristic absorption bands of the PDI core at 533, 498 and 465 nm, associated with the 0 →
0, 0 → 1 and 0 → 2 vibrational modes of the perylene core, respectively (Figure 2 d).18 In compar-
ison, the UV-Vis spectrum of AzaBPDI 11 exhibits a blue shift with a maximum band at 485 nm.
The latter was juxtaposed with the dyads spectra (in orange in Figure 2). The UV-Vis spectrum of
dyad 7 compared to that of reference 11, displays a hypsochromic shift accompanied by a broad
and very weak band from 500 to 650 nm, presumably an intramolecular charge transfer band (ICT)
such as for its PDI-TPA analog.19 The absorption profil of AzaBPDI-Fl 8 exhibits an enlargement
of the bands, as previously observed for AzaBPDI attached with donor units,13 suggesting elec-
tronic interaction at the ground state between the two photoactive units. On the contrary, the spectra
of AzaBPDI-PDI 9 and AzaBPDI-PMI 10 correspond to the linear combination of the two units
spectra. Indeed, dyads 9 and 10 absorb between 400 and 550 nm with distinct peaks at 430 and 476
nm characteristic of the AzaBPDI chromophoric unit and 520 and 533 nm for PMI and PDI units,
respectively. UV-Vis spectra of thin films show a red-shift of the absorption maxima for compound
9 and 10, and their coverage of the visible spectrum is extended beyond 600 nm (see S.I., Figure
S21). All together, the optical properties of dyads 9 and 10 demonstrate that they could be of par-
ticular interest for applications of as NFAs in OSCs.
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Regarding the fluorescence properties, the parent chromophoric units AzaBPDI 11, PDI-CHO 5
and PMI-CHO 6 display very high quantum yields (Φfl) from 0.9 to 1. When attached to the second
unit, the quantum yield of dyads strongly varied according to their molecular design. While
AzaBPDI-PDI 9 displays a good yield Φfl = 0.88, the fluorescence of AzaBPDI-TPA 7 or
AzaBPDI-PMI 10 is quasi-totally quenched with Φfl = 0 and 0.04, respectively, suggesting the
presence of intramolecular quenching mechanisms. Considering that into dyads 9 and 10, the chro-
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mophoric units do not electronically interact at the ground state, in addition with the complemen-
tarity of the spectral properties of AzaBPDI and PMI/PDI, intramolecular energy transfer (EnT)
processes within dyads 9 and 10 were investigated using steady-state fluorescence spectroscopy
(Figure 3).
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Figure 2. UV-Vis absorption spectrum of AzaBPDI 11 juxtaposed with that of a) AzaBPDI-TPA
7; b) AzaBPDI-Fl 8; c) AzaBPDI-PDI 9, PDI-CHO 5; d) AzaBPDI-PMI 10, PMI-CHO 6 in CHCl3.
Molar extinction coefficients were determined from five different concentrations (10-5-10-6 M).
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Table 1. UV-Vis absorption (10-5 M) and emission (10-6 M) data of references 5, 6 and 11, dyads
7, 8, 9 and 10 in CHCl3.
9
ꢀꢁꢂꢃꢄ(nm)
ꢀꢂꢅ ꢃꢄ(nm)
ꢀ
(nm)
ꢂꢃꢄ
ꢇꢈꢊꢉꢈ ꢋꢌꢍ
a
Compound
Ɛ1/104 (M-1cm-1)
Ɛ2/104 (M-1cm-1)
ꢆꢂ
Φfl
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PDI-CHO 5
533
520
465
481
535
4.2
3.7
5.7
3.1
4.2
3.7
5.6
498
495
435
434
476
476
446
2.9
3.7
4.1
3.1
6.0
6.0
3.1
570
555
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0.95 2.25
1.00 2.31
PMI-CHO 6
AzaBPDI-TPA 7
AzaBPDI-Fl 8
AzaBPDI-PDI 9
0.00
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554
583
563
489
0.55 2.45
0.88 2.23
0.04 2.28
0.90 2.58
AzaBPDI-PMI 10 520
AzaBPDI 11 476
a Determined with Rhodamine 101 (Φfl = 1 in MeOH).20
b Determined by the intersection λ0-0 of the normalized absorption and emission spectra according to E0-0 = 1240/λ0-0
.
The complementary spectral properties of AzaBPDI and PDI/PMI units depicted in Figure 2a, sug-
gests that a Förster Resonance type Energy Transfer mechanism,21 can occur within dyads 9 and
10 as the emission spectrum of AzaBPDI 11 perfectly overlaps with the absorption spectra of PDI
5 and PMI 6. In this respect, AzaBPDI units can act as an energy donor and PDI/PMI units as
energy acceptors. Moreover, the donor and acceptor units absorb and emit at distinct wavelength
and can be selectively excited. Hence, the efficiency of the energy transfer EnT can be quantified
using steady-state techniques following two methods.22
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Figure 3. a) Complementary normalized absorption and fluorescence spectra of PDI-CHO 5, PMI-
CHO 6 and AzaBPDI 11. Fluorescence emission spectra of b) AzaBPDI-PDI 9 and d) AzaBPDI-
PMI 10 by selective excitation of donor AzaBPDI (exc = 430 nm) and acceptor PDI/PMI (exc
=
500 nm); Fluorescence excitation (emis = 620 nm) and absorption spectra normalized on max ac-
ceptor of c) AzaBPDI-PDI 9 and e) AzaBPDI-PMI 10.
First, emission spectra can be used, by determining the ratio of quantum yield of the acceptor unit
by selective excitation of the donor (exc = 430 nm) affording its sensitized quantum yield, and
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direct excitation of the acceptor (exc = 500 nm): EnT = Φ*fl (A) / Φfl (A). According to this strategy,
the energy transfer appears to be very efficient, with yields of 95% within dyad 9 and 79% within
10 for its remaining fluorescence. Those results are in agreement with the quenched emission of
the donor units when dyads were excited at 430 nm. Besides, these can be confirmed by recording
the excitation spectrum of the derivatives at the selective emission wavelength of the acceptor units
(emis = 620 nm), normalizing it with their absorption on max acceptor, and comparing the intensity
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of the donor at 430 nm: EnT = Exc(D)/Abs (D). Indeed for dyad 9, an efficiency of 95% was calculated
whereas 81% was found for dyad 10. The quenching of fluorescence in dyad 10 cannot be explained
by these experiments and would require further investigations by transient absorption (TA) spec-
troscopy, to explore various hypotheses such as a photoinduced electron transfer (PET) or the con-
version into a triplet state via intersystem crossing (ISC).
The electrochemical properties of the four dyads were investigated by cyclic voltammetry (CV) in
deaerated CH2Cl2, or CH2Cl2/Chlorobenzene (1:1) for lower soluble products, and in the presence
of Bu4NPF6 as supporting electrolyte (Figure 4). PDI 5, PMI 6 and AzaBPDI 11 compounds were
used as references to determine the nature of reduced species. As previously reported, AzaBPDI
based compounds display slightly lower reduction potentials than PDI derivatives.11 Dyads 7 and
8 showed the expected two reversible one-electron reduction waves around E1red = – 1.2 V and E2
red
= – 1.4 V vs Fc+/Fc comparable to that of AzaBPDI 11, corresponding to the successive formation
-
of AzaBPDI. and AzaBPDI2- species, respectively. A reversible oxidation wave was observed for
AzaBPDI-TPA 7 at E1ox = + 0.61 V vs Fc+/Fc and attributed to the oxidation of the TPA unit,
whereas no oxidation waves were detected for reference 11 and an irreversible oxidation wave at
+ 0.91 V was found for dyad 8 (see S.I., Figure S23).
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By comparison with references PMI 5, PMI 6 and AzaBPDI 11, we assigned the electrochemical
processes for both dyads AzaBPDI-PDI 9 and AzaBPDI-PMI 10. Compound 9 showed three re-
versible reduction waves (Figure 4a). The first reduction process of PDI and that of AzaBPDI are
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overlapping leading to AzaBPDI. -PDI. species. Following this two-electron process at E1 = –
red
1.14 V vs Fc+/Fc, two one-electron reduction waves are observed at – 1.29 and – 1.42 V corre-
sponding to the generation of AzaBPDI. -PDI2- and AzaBPDI2--PDI2- species, respectively.
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AzaBPDI-PMI 10 showed three reversible reduction waves with a first one-electron process at E1
red
= – 1.20 V vs Fc+/Fc corresponding to the formation of AzaBPDI. -PMI species (Figure 4b). The
-
second two-electron wave at E2 = – 1.45 V arises from the concomitant second reduction of
red
-
AzaBPDI unit and the first reduction of PMI leading to the AzaBPDI2--PMI. species. Finally, the
last one-electron reduction wave at E3red = – 1.92 V corresponds to the AzaBPDI2--PMI2- species.
Using the reduction potentials coupled with the optical properties, the molecular orbital frontiers
were calculated and are depicted in Table 2.
Figure 4. Cyclic voltammograms (CV) in Bu4NPF6 (0.1 M), CH2Cl2 (for 5, 6 and 11) or
CH2Cl2/Chlorobenzene (1:1) (for 9 and 10), 100 mV/s of a) AzaBPDI 11, PDI-CHO 5 and
AzaBPDI-PDI 9; b) AzaBPDI 11, PMI-CHO 6 and AzaBPDI-PMI 10.
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Table 2. Redox potential values
a Calculated from ELUMO= - (E1red + 4.8) with E1red being the half-wave potential of the first reduction wave. The LUMO values were calculated with
respect to ferrocene (reference energy level = 4.8 eV below the vacuum level).
b Calculated using the following equation: EHOMO = ELUMO- E0-0, cor using the following equation EHOMO= -(E1ox + 4.8) with E1ox being the half-wave
potential of the first oxidation wave.
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Compounds
E1 [V vs. Fc+/Fc]
red
E2 [V vs. Fc+/Fc]
red
E3 [V vs. Fc+/Fc] E1 [V vs. Fc+/Fc]
ELUMO/eVa EHOMO/eV
red
ox
PDI-CHO 5
- 1.05
- 1.41
- 1.17
- 1.21
- 1.24
- 1.77
- 1.38
- 1.42
- 3.75
- 3.39
- 3.63
- 3.59
- 6.00 b
- 5.70 b
- 5.41c
-5.71c
PMI-CHO 6
AzaBPDI-TPA 7
AzaBPDI-Fl 8
+ 0.61
+ 0.91
AzaBPDI-PDI 9
AzaBPDI-PMI 10
AzaBPDI 11
- 1.14
- 1.20
- 1.16
- 1.29
- 1.45
- 1.38
- 1.42
- 1.92
- 3.66
- 3.60
- 3.64
-5.89b
- 5.88b
- 6.22b
Furthermore, DFT calculations were performed on dyads 9 and 10. In their optimized geometry,
the two chromophoric units were found to be almost perpendicular to each other (with dihedral
angles of 99° and 79° for 9 and 10, respectively). This is of great interest as it has been demon-
strated that a large dihedral angle into PDI dimers reduces their aggregation and favors their good
performance as NFAs in OSCs.4a, 23 The frontier molecular orbitals of 9 and 10 were also computed
(Figure 5 and Calculation reports). For dyad 9, the HOMO is fully located on the PDI unit with an
energy level of –5.85 eV and the LUMO is predominant on the PDI unit as well (-3.41 eV). In
contrast, for dyad 10, the HOMO is centered on the PMI (-5.81 eV) whereas the LUMO on the
AzaBPDI (-3.40 eV). Those predictions are in accordance with the experimental findings, and the
energetic offset can be presumably attributed to solvents effects as the calculations were performed
in gas phase.
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Figure 5. Representation of the a) HOMO and b) LUMO of dyad 9 and c) HOMO and d) LUMO
of dyad 10 from different points of view, determined by theoretical calculations (see Molecular
Calculation Report).
Conclusion
In conclusion, we have exploited our recently developed visible-light-mediated synthesis of
AzaBPDI for preparation of four unprecedented chromophoric dyads in very good yields. This
approach was advantageously compared to the well-known Pictet-Spengler type-reaction inspired
from reported procedures. Moreover, these results clearly demonstrate that this new procedure can
be extended to more complex aldehyde substrates rather than those we initially described. This
strategy illustrates that the AzaBPDI unit behaves as an excellent platform for promoting energy
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or electron transfer within multichromophoric architectures. Such dyads could also find applica-
tions in OLEDs24 or thermally-assisted delayed fluorescence (TADF) material25. Moreover, con-
sidering the extension of absorption coverage of dyads 9 and 10 in comparison with PDI dimers
described in literature, their incorporation in organic solar cells as non-fullerene acceptors seems
promising. These studies are undergoing, in addition with the preparation of more complex
AzaBPDI-based architectures using this original synthetic strategy.
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Experimental section
Materials and General Methods. Thin Layer Chromatography (TLC) was conducted on pre-
coated aluminum sheets with 0.20 mm MerckAlugram SIL G/UV254 with fluorescent indicator
UV254. Column chromatography was carried out using Sigma-Aldrich silica gel 60 (particle size
63-200 µm). UV-Vis absorption spectra were recorded on a Shimadzu UV-1800 UV-Vis spectro-
photometer using quartz cell (pathlength of 1 cm). Thin-films were prepared by spin-coating 1 %
or 0.5% wt/v solutions from CHCl3 or chlorobenzene onto Corning glass micros slides. Prior to
use, glass slides were cleaned with soap and water, acetone and isopropanol, and followed by
UV/ozone treatment using a Novascan UV/ozone cleaning system. Fluorescence was measured on
a Shimadzu RF-6000 Spectrophotometer using quartz cell (pathlength of 1 cm). Cyclic voltamme-
try experiments were carried out at room temperature with a Bio-Logic SAS SP-150 potentiostat.
The working electrode is a platinum electrode, the counter electrode a platinum wire and the
AgCl/Ag electrode was used as reference. The HOMO/LUMO energy levels calculated were ref-
erenced with the energy level of ferrocene (4.8 eV below the vacuum). NMR spectra were recorded
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13
using Bruker 300 MHz spectrometer (300 MHz for H and 75 MHz for C) and 500 MHz spec-
trometer (500 MHz for 1H and 125 MHz for 13C). Chemical shifts are reported in ppm (δ) relative
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to the solvent residual signal (CDCl3: = 7.26 ppm, C= 77.16 ppm; Cl2CDCDCl2: = 6.00
8
9
ppm, C= 73.78 ppm). Coupling constants (J) were given in Hz. Resonance multiplicity was de-
scribed as s (singlet), d (doublet), t (triplet), dd (doublet of doublets), m (multiplet) and br (broad
signal). Carbon spectra were acquired with a complete proton decoupling 13C{1H}. MALDI-TOF
spectra were performed on a Bruker Daltonics Biflex III using DCTB (trans-2-[3-(4-tert-Bu-
tylphenyl)-2-methyl-2-propenylidene]malononitrile) as matrix. High resolution mass spectrometry
(HRMS-FAB) was performed with a JEOL JMS-700 B/E using m-nitrobenzylic alcohol as matrix.
Photocyclizations were carried out by introducing the reaction flasks in a homemade photoreactor
consisting of a plastic cylinder in which the inside wall was covered by a 1.5 meter white LEDs
ribbon (~ 100 LEDs), power of 7 W. The light sources were placed 5 cm away from the reactor.
Gaussian (09 revision D.01) was used to perform the DFT calculations. Detailed results for all
modelled compounds can be found in the attached “Molecular Calculation Report”. Chemicals
were purchased from Sigma Aldrich, Acros Organics, Fisher Scientific, Alfa Aesar, Fluorochem,
and were used as received. Solvents were purchased from Sigma Aldrich, Fluorochem, or Fischer
Scientific while deuterated solvents from Sigma Aldrich. 1-AminoPDI 2 was prepared according
to the literature.9c
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Abbreviations. AzaBPDI : AzaBenzannulatedPerylenediimide; DDQ : 2,3-dichloro-5,6-dicyano-
benzoquinone; DFT : density functional theory; DMF: N,N-dimethylformamide; EnT: energy
transfer; Fl : fluorene; HOMO : highest occupied molecular orbital; HRMS : high resolution mass
spectrometry; LUMO : lowest unoccupied molecular orbital; NMR : Nuclear Magnetic Resonance;
PDI : perylenediimide; PET: photoinduced electron transfer; PMI : perylenemonoimide; rt : room
temperature; TFA : Trifluoroacetic Acid; TLC: Thin Layer Chromatography; TPA: triphenyla-
mine.
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General procedures for syntheses of AzaBPDI based dyads:
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Method A (Light-mediated imine photocyclization): 1-AminoPDI 2 (100 mg, 0.18 mmol or 50
mg, 0.09 mmol), aldehyde 3-6 (3 or 1.1 equiv.), and activated molecular sieves (3Å) (if 1.1 equiv.
of aldehyde) were placed in a Schlenk flask along with dry solvent (CH2Cl2 or DMF) (0.012 M).
The mixture was degassed by bubbling argon for 5 min before the addition of trifluoroacetic acid
(around 1 mmol). The mixture was stirred at 50 °C in CH2Cl2 (or 130 °C in DMF) for 1h (to 17 h)
using a heating mantle. After cooling down, the reaction mixture was subsequently diluted in
CH2Cl2 (400 mL) before being exposed to visible light (white light, 7 W) for ̴ 1h30 until complete
disappearance of the imine according to TLC. DDQ (1 equiv.) was then added and the resulting
mixture was stirred at room temperature for 5 (compound 7, 8 and 11) to 30 min (dyads 9 and 10)
according to the solubility of the material. The solvents were removed under vacuum and the resi-
due was purified on column chromatography (SiO2, CH2Cl2 to CH2Cl2/MeOH) to provide
AzaBPDI dyads, which were further precipitated from CH2Cl2/Petroleum Ether (or Et2O).
Method B (Pictet-Spengler type reaction): 1-AminoPDI 2 (150 mg, 0.18 mmol), aldehyde 3-6
(6 or 1 equiv), and activated molecular sieves (3Å) were placed in a Schlenk flask along with dry
DMF (25 to 45 mL according to the solubility of the aldehyde). The mixture was degassed by
bubbling argon for 30 min before the addition of triflic acid (1.8 mmol). The reaction mixture was
stirred at 130 °C under argon atmosphere for 3 h using a heating mantle. Subsequently, DDQ (1
equiv) was added and/or the inert atmosphere was replaced by pure oxygen, and the reaction mix-
ture was heated after under reflux for 24 h. The reaction mixture was quenched by addition of water
and neutralized with 15% NaOH solution. The organic phase was extracted, washed again two
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times with water and brine, dried with MgSO4 and concentrated. Purification protocol described in
Method A was applied.
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AzaBPDI-TPA dyad (7). The compound was prepared according to the general procedures. Method
A: Using 1-aminoPDI 2 (100 mg, 0.18 mmol), 4-(diphenylamino)benzaldehyde 3 (145 mg, 0.53
mmol) in CH2Cl2 (step 1/ 15 mL and step 2/ 400 mL). After purification through column chroma-
tography (SiO2, CH2Cl2 to CH2Cl2/MeOH 99:1), and precipitation, AzaBPDI-TPA 7 was obtained
(113 mg; 77%) as a brown solid. Method B: Using 1-aminoPDI 2 (200 mg, 0.35 mmol), 4-(diphe-
nylamino)benzaldehyde 3 (574 mg, 2.1 mmol) in dry DMF (30 mL) and DDQ (80 mg, 0.35 mmol)
1
for the re-aromatization step to afford AzaBPDI-TPA 7 (133 mg; 46%). H NMR (CDCl3, 500
MHz): δ (ppm) = 9.32 (s, 1H), 9.11 (s, 1H), 8.71 (d, J = 8.1 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.60
̶
8.57 (m, 2H), 7.80 (d, J = 8.4 Hz, 2H), 7.42 7.33 (m, 10H), 7.19
̶
̶ 7.17 (t, 2H), 5.14 ̶ 5.09 (m, 2H),
2.69 2.60 (m, 4H), 2.02 ̶ 1.95 (m, 8H), 1.83-1.80 (m, 2H), 1.57 ̶
̶
1.38 (m, 6H). 13C{1H} NMR (125
MHz, CDCl3) δ (ppm) =163.7, 163.6, 163.4, 160.4, 149.8, 147.2, 143.9, 134.2, 133.2, 132.2, 132.2,
131.4, 130.6, 130.2, 129.8, 128.6, 128.4, 127.4, 126.0, 125.8, 125.6, 124.2, 123.5, 123.2, 123.0,
122.6, 122.1, 122.0, 121.9, 121.1, 117.2, 54.7, 54.6, 29.3, 26.8, 25.7, 25.7. HRMS (FAB+) m/z :
[M]+ calcd for C55H42N4O4: 822.3201; found: 822.3219.
AzaBPDI-Fl dyad 8. The compound was prepared according to the general procedures. Method A:
Using 1-aminoPDI 2 (100 mg, 0.18 mmol), 2-fluorenecarboxaldehyde 4 (103 mg, 0.53 mmol) in
CH2Cl2 (step 1/ 1h30 in 15 mL and step 2/ 400 mL). After purification through column chromatog-
raphy (SiO2, CH2Cl2 to CH2Cl2/MeOH 99:1), and precipitation, AzaBPDI-Fl 8 was obtained (112
mg; 84%) as a yellow solid. Method B: Using 1-aminoPDI 2 (150 mg, 0.26 mmol), 2-fluorenecar-
boxaldehyde 4 (408 mg, 2.1 mmol) in dry DMF (30 mL) and pure oxygen for the re-aromatization
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step to afford AzaBPDI-Fl 8 (70 mg; 35%). 1H NMR (Cl2CDCDCl2, 500 MHz, 353 K): δ (ppm) =
9.60 (s, 1H), 9.58 (s, 1H), 9.25 (d, J = 9.3 Hz, 1H), 9.24 (d, J = 9.3 Hz, 1H), 9.11 (d, J = 9.1 Hz,
1H), 9.06 (d, J = 9.1 Hz, 1H), 8.24 (s, 1H), 8.15 (d, J = 8.1 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.99
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(d, J = 8.0 Hz, 1H), 7.69 (d, J = 7.7, 1H), 7.53 (t, J = 7.5, 1H), 7.46 (t, J = 7.5, 1H), 5.21
̶ 5.13 (m,
2H), 4.20 (s, 2H), 2.75 ̶ 2.63 (m, 4H), 2.04 ̶ 1.80 (m, 10H), 1.53 ̶
1.40 (m, 6H). 13C{1H} NMR (125
MHz, 353 K, Cl2CDCDCl2) δ (ppm) = 163.8, 163.7, 163.6, 161.3, 144.3, 143.9, 143.8, 143.2,
140.7, 136.6, 134.6, 134.1, 132.5, 130.6, 129.9, 129.1, 129.1, 128.0, 127.5, 127.5, 127.0, 126.3,
126.3, 125.1, 124.0, 123.6, 123.6, 123.2, 123.0, 122.8, 122.6, 121.9, 120.4, 120.0, 99.5, 54.5, 37.2,
29.2, 29.2, 26.5, 26.5, 25.4, 25.4. HRMS (FAB+) m/z : [M + H]+ calcd for C50H38N3O4: 744.2862;
found: 744.2866.
AzaBPDI-PDI dyad (9). The compound was prepared according to the general procedures. Method
A: Using 1-aminoPDI 2 (50 mg, 0.09 mmol), 1-(4-formylphenyl)PDI8a 5 (66 mg, 0.1 mmol) in
DMF (step 1/ 17 h in 7 mL) and CH2Cl2 (step 2/ 400 mL). After purification through column
chromatography (SiO2, CH2Cl2 to CH2Cl2/MeOH 97:3), and precipitation, AzaBPDI-PDI 9 was
obtained (75 mg; 69%) as a dark red solid. Method B: Using 1-aminoPDI 2 (150 mg, 0.26 mmol),
1-(4-formylphenyl)PDI 5 (171 mg, 0.26 mmol) in dry DMF (45 mL) and pure oxygen for the re-
1
aromatization step to afford AzaBPDI-PDI 9 (54 mg; 25%). H NMR (CDCl3, 500 MHz): δ (ppm)
= 9.63 (s, 1H), 9.62 (s, 1H), 9.31 (d, J = 8.3 Hz, 1H), 9.30 (d, J = 8.3 Hz, 1H), 9.15 ( d, J = 8.2 Hz,
1H), 9.10 (d, J = 8.2 Hz, 1 H), 8.74
̶ 8.71 (m, 2H), 8.67 ̶ 8.65 (m, 2H), 8.62 (d, J = 8.1 Hz, 1H),
8.47 (d, J =8.2 Hz, 1H), 8.24 (d, J = 8.3 Hz, 1H), 8.18 ( d, J = 8.1 Hz, 2 H), 7.89 ( d, J = 8.1 Hz,
2H), 5.11
̶
5.06 (m, 2H), 5.03
̶ 4.97 (m, 2H), 2.73 ̶ 2.64 (m, 4H), 2.62 ̶ 2.49 (m, 4H), 2.00 ̶ 1.69 (m,
20H), 1.52
̶
1.37 (m, 12H). Due to the low solubility of compound 9, 13C NMR spectrum could not
be recorded. HRMS (MALDI) m/z : [M]+ calcd for C79H61N5O8: 1207.4520; found: 1207.4520.
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AzaBPDI-PMI dyad (10). The compound was prepared according to the general procedures.
Method A: using 1-aminoPDI 2 (50 mg, 0.09 mmol), 9-(4-formylphenyl)PMI17 6 (59 mg, 0.1
mmol) in DMF (step 1/ 17 h in 7 mL) and CH2Cl2 (step 2/ 400 mL). After purification through
column chromatography (SiO2, CH2Cl2 to CH2Cl2/MeOH 97:3), and precipitation, AzaBPDI-PDI
10 was obtained (80 mg; 79%) as a brown solid. Method B: Using 1-aminoPDI 2 (100 mg, 0.18
mmol), 9-(4-formylphenyl)PMI 6 (119 mg, 0.18 mmol) in dry DMF (30 mL) and pure oxygen for
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the re-aromatization step to afford AzaBPDI-PMI 10 (80 mg; 41%). H NMR (CDCl3, 500 MHz,
323 K): δ (ppm) = 9.61 (s, 2H), 9.10-9.09 (m, 2H), 9.03 (d, J = 9.0, 1H), 8.99 (d, J = 9.0, 1H), 8.59
(d, J = 8.6 Hz, 1H), 8.54 (d, J = 8.5 Hz, 1H), 8.27
̶
J = 7.7 Hz, 1H), 7.54-7.49 (m, 2H), 7.40 (d, J = 7.4 Hz, 2H), 5.29
̶
̶
2H), 2.77
̶
2.70 (m, 4H), 2.06
̶
1.93 (m, 8H), 1.87
̶
1.80 (m, 2H), 1.59 (br, 4H), 1.45 (m, 2H), 1.33 ̶
13
1.24 (m, 12H). Due to the low solubility of compound 10, C NMR spectrum could not be rec-
orded. HRMS (FAB+) m/z : [M]+ calcd for C77H58N4O6: 1134.4351; found: 1134.4363.
AzaBPDI 11. The compound was prepared according to the general procedures. Method A: using
1-aminoPDI 2 (100 mg, 0.18 mmol), benzaldehyde (191 mg, 1.8 mmol) in CH2Cl2 (step 1/ 15 mL
and step 2/ 400 mL). After purification through column chromatography (SiO2, CH2Cl2 to
CH2Cl2/MeOH 99:1), and precipitation, AzaBPDI 11 was obtained (98 mg; 83%) as a yellow solid.
Method B: Using 1-aminoPDI 2 (200 mg, 0.35 mmol), benzaldehyde (222 mg, 2.1 mmol) in dry
DMF (30 mL) and pure oxygen for the re-aromatization step to afford AzaBPDI-PMI 10 (79 mg;
1
34%). H NMR (CDCl3, 500 MHz): δ (ppm) = 9.51 (s, 1H), 9.50 (s, 1H), 9.16
̶
9.14 (m, 2H), 9.04
(d, J = 8.2 Hz, 1H), 8.99 (d, J = 8.1 Hz, 1H), 7.99 7.97 (m, 2H), 7.76
̶
̶ 7.68 (m, 3H), 5.20 ̶ 5.10 (m,
2H), 2.71 2.59 (m, 4H), 1.98 1.77 (m, 10H), 1.55 ̶
̶
̶
1.33 (m, 6H). 13C{1H} NMR (125 MHz, CDCl3)
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δ (ppm) = 164.2, 164.0, 164.0, 163.9, 161.5, 144.5, 138.4, 134.9, 134.2, 132.6, 132.5, 131.0, 130.9,
130.0, 129.4, 129.3, 129.2, 128.1, 126.5, 126.4, 124.2, 123.8, 123.7, 123.5, 123.0, 122.9, 122.7,
122.0, 118.6, 54.6, 29.4, 29.4, 26.8, 25.6. HRMS (FAB+) m/z : [M + H]+ calcd for C43H34N3O4:
656.2549; found: 656.2529.
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Computational Details. For dyads 9 and 10, geometric optimizations followed by frequency cal-
culations have been performed. We chose a hybrid DFT approach, with the B3LYP functional,
particularly reliable for geometries and energies. The basis set used is in agreement to an aug-
mented double zeta, 6-31+G(2d,p). The grid used corresponds to the default parameters of the
Gaussian09 program. The TD-DFT excited states calculations were set with the same parameters.
Although not optimized for TD-DFT, the B3LYP gave a reasonable estimation for singlet states
energies. Here, 15 states were computed and all full reports have been included in supplementary
information.
ASSOCIATED CONTENT
Supporting Information
Supporting Information Available: NMR and MS spectra, supplementary spectroscopic data, cyclic
voltammetry results.
AUTHOR INFORMATION
Corresponding Author
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*E-mail: pietrick.hudhomme@univ-angers.fr
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ACKNOWLEDGMENTS
Angers Loire Métropole (ALM) and the University of Angers are acknowledged for a PhD grant
to Rayane El-Berjawi (program RFI Lumomat). We gratefully acknowledge the SFR MATRIX,
University of Angers, with Dr. Ingrid Freuze and Sonia Jerjir for their assistance in mass spectro-
metry experiments and Eric Levillain for his help regarding the cyclic voltammetry experiments.
NOTES
Lou Rocard: 0000-0003-1692-8391
Antoine Goujon: 0000-0002-8689-1021
Thomas Cauchy: 0000-0003-4259-3257
Piétrick Hudhomme : 0000-0002-7383-9603
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