Tuning the LUMO Levels of Z-Shaped Perylene Diimide via Stepwise Cyanation

Article abstract of DOI:10.1021/acs.joc.1c00399

The central dogma in constructing organic electron acceptors is to attach electron-withdrawing groups to polycyclic aromatic hydrocarbons. Yet, the full potentials of many organic acceptors were never realized due to synthetic obstacles. By combining the

Full text of DOI:10.1021/acs.joc.1c00399

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Tuning the LUMO Levels of Z‑Shaped Perylene Diimide via Stepwise
Cyanation
Bhargava Rao Billa and Chih-Hsiu Lin*
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ABSTRACT: The central dogma in constructing organic electron
acceptors is to attach electron-withdrawing groups to polycyclic
aromatic hydrocarbons. Yet, the full potentials of many organic
acceptors were never realized due to synthetic obstacles. By
combining the Wittig−Knoevenagel benzannulation, the Pd(0)-
catalyzed cyanation, and nucleophilic addition/oxidation cyana-
tion, six polynitrile Z-shaped perylene diimide were synthesized.
These stable and soluble electron acceptors possess LUMO energy
levels comparable with those of benchmark compounds. Electro-
chemical investigation reveals that each additional nitrile group
reduces the LUMO energy by 0.2 eV.
unique advantages of polynitrile PAHs as electron accept-
ue to the global demand for a new generation of
Drenewable and miniaturized technology, the curiosity- ors.4f−h However, the current synthetic strategies toward aryl
imide and aryl nitriles lack the scope and adaptability to put
multiple imide and nitrile groups on one PAH core. For
example, the most common precursors to aryl nitriles are
corresponding aryl halides via the classic Rosenmund−von
Braun cyanation5 or its Pd(0)-catalyzed modern version.6 Yet,
the regioselective synthesis of polyhalogenated PAHs is itself a
formidable challenge.7 As for the nontrivial synthesis of aryl
imide (where the starting compound is not an anhydride),
there are only a few reports in the literature.8 These synthetic
limitations obstruct the accessibility of many potential
materials.
In the past two decades, the 3,4,9,10-perylene diimide (PDI)
emerged as a versatile structural motif in the pursuit of organic
electron acceptors.3a−e The application of this century-old
chromophore is not impeded by the aforementioned synthetic
obstacles because its anhydride precursor is commercially
available. The 3,4,9,10-PDI scaffold so dominates the field that
the abbreviation PDI becomes synonymous with this linear
isomer. On the other hand, 1,2,7,8-PDI, the Z-shaped isomer,
is almost entirely ignored due to the lack of synthetic and
commercial accessibility. However, the Z-shaped PDI has a few
advantages over its linear cousin as a scaffold for further
functionalization. First, with the imide carbonyl oxygen atoms
driven research of redox-active conjugated systems has evolved
into the quest for organic electronic materials. The innovated
materials have found applications in large-area and flexible
devices like field-effect transistors (OFETs), light-emitting
diodes (OLEDs), magnetic materials, and solar cells.1
However, constructing stable electron-accepting n-type organic
materials is far more difficult than their p-type counterparts
because of the intrinsic low electron affinity of carbon 2p
orbitals. The endeavor to design and synthesize new organic
electron acceptors not only provides new materials but also
helps researchers to better comprehend the relationship
between molecular structures and electronic properties.
Ambient stable n-type materials usually possess low LUMO
energy levels to ensure effective electron injection. The radical
anion thus produced should also be stable to moisture and
oxygen to prevent degradation. However, acceptors with low
LUMO levels could become susceptible to reduction or
nucleophilic attacks.2 Such stability problems would limit the
scope of these acceptors in device applications. To successfully
negotiate the delicate balance between electron-accepting
capacity and stability, the stepwise tuning of LUMO levels
seems a more practical approach than simply minimizing the
LUMO.
The prerequisite of electron acceptors is that the LUMO
energy levels should be sufficiently low to accommodate
injected electrons. The most straightforward approach is to
install electron-withdrawing substitutions to polycyclic aro-
matic hydrocarbons (PAHs). Among various electron-with-
drawing groups, imide3 and nitrile4 are the most frequently
employed for this purpose. Theoretical studies revealed some
Received: February 18, 2021
Published: July 2, 2021
https://doi.org/10.1021/acs.joc.1c00399
© 2021 American Chemical Society
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residing in the bay area, the perylene skeleton adopts a twist
conformation. Such a nonplanar architecture prevents the π−π
stack interactions in solid packing, thereby improving their
solubilities. Furthermore, there are only two types of
derivatization sites (ortho and bay as shown in Figure 1a) in
catalyzed (DBU) Knoevenagel cyclization then furnishes the
aryl imide. This benzannulation protocol has enabled the de
novo construction of many hitherto inaccessible PAH
derivatives. The nucleophilic addition/oxidation cyanation
requires electron-deficient substrates to first react with cyanide
anion. The intermediate anion is then oxidized (aromatized) to
give the aryl nitrile. Unlike the Rosenmund−von Braun
cyanation, this protocol does not require aryl halides as its
starting materials. It thereby offers more strategic flexibility in
the synthesis of polynitrile PAHs.
The first task is to synthesize the 1,2,7,8- PDI skeleton. The
Z-shaped perylene derivative was first synthesized in 2005 with
Norrish type photochemical cycloaddition as its key step.11 We
later devised a more scalable synthesis using Wittig−
Knoevenagel benzannulation.12 As shown in Scheme 2, the
starting material 1,5-diiodoanthraquinone was first styrylated
with a Heck coupling reaction. The aldehyde-ketone synthon
required for the key benzannulation step was unveiled after
ozonolysis. The 2-fold Wittig−Knoevenagel benzannulation
(maleimide + triethyl phosphine/1,8-diazabicyclo[5,4,0]-
undec-7-ene (DBU)) then furnished the Z-shaped PDI 3.
The peri positions of 3 were brominated (N-bromosuccina-
mide (NBS)/trifluoroacetic acid(TFA)) to give dibromide 4.
The first stage of cyanation was then accomplished with Pd(0)-
c a t a l y z e d c y a n a t i o n ( P d 2 ( D B A ) 3 , 1 , 1 ′ b i s -
(diphenylphosphino)ferrocene (dppf), Zn(CN)2) to produce
5. After the two nitrile groups are installed, the perylene core of
5 is electron-deficient enough to undergo direct nucleophilic
addition by cyanide anion (tetrabutylammonium cyanide,
TBACN). The anion thus produced is readily oxidized by
atmospheric oxygen to restore the perylene skeleton in the
Figure 1. Derivatization sites in linear and Z-shaped perylene diimide
(PDI).
the linear PDI skeleton. Because it is difficult to differentiate
the reactivity of these sites, selective or stepwise functionaliza-
tion poses a daunting challenge. In contrast, the Z-shaped PDI
possesses four types of sites (peri (a), peri (b), ortho, and bay
in Figure 1b) with distinctive reactivities. By judiciously
arranging the reaction sequence, regiochemical controlled
functionalization seems feasible. By exploiting the aforemen-
tioned advantages of the Z-shaped PDI scaffold, we hereby
report the preparation and characterization of polynitrile Z-
shaped PDI as a class of stable, soluble, and tunable electron
acceptors. Preliminary investigations of their photophysical and
electrochemical properties are also presented.
The key synthetic reactions used in this report are the
Wittig−Knoevenagel benzannulation9 and nucleophilic addi-
tion/oxidation cyanation10 (Scheme 1a,b). In the benzannu-
lation reaction, the maleimide first undergoes Michael addition
with trialkyl phosphine to generate a Wittig reagent which
reacts with an ortho-keto aryl aldehyde. A subsequent base-
1
trinitrile 6. The H NMR of 6 (with two pairs of doublet
signals and a singlet in the aromatic region) validates the
cyanide attack takes place exclusively at the peri position.
When 5 was treated with 2.5 equiv of TBACN, tetranitrile 7
was produced. Again, judging from its 1H NMR spectrum, the
cyanide attacks the peri position exclusively to result in the
3,4,9,10 tetranitrile 7.
When this protocol was repeated to introduce another nitrile
substitution to the Z-shaped PDI, no desired product was
observed. Another cyanation route was therefore devised as
depicted in Scheme 3. When the bromination step in Scheme 2
Scheme 1. Key Synthetic Reaction to Furnish Z-Shaped PDI Polynitrile: (a) Wittig−Knoevenagel Benzannulation and (b)
Nucleophilic Addition/Oxidation Cyanation
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a
Scheme 2. Synthesis of Z-Shaped PDI with Nitrile Substituents at Peri Positions
a
Reagents and conditions: (a) styrene, (MeCN)2PdCl2, TBABr, Et3N, toluene, 64%; (b) ozone, −78 °C, dimethyl sulfide, 78%; (c) n-dodecyl
maleimide, PEt3, then DBU, 65%; (d) NBS, TFA, CH2Cl2 (4:1), 16 h, 56%; (e) Zn(CN)2, 1,1′-bis(diphenylphosphino)ferrocene (dppf),
Pd2(dba)3, dioxane, 71%; (f) 1.2 equiv of TBACN, toluene, 41%; (g) 2.5 equiv of TBACN, toluene, 38%.
a
Scheme 3. Synthesis of Z-Shaped PDI with Nitrile Substituents at Peri and Bay Positions
a
Reagents and conditions: (a) NBS, TFA/CH2Cl2 (4:1), 22% of 8 and 34% of 9; (b) Zn(CN)2, dppf, Pd2(dba)3, dioxane, 53%; (c) TBACN,
toluene, 68%.
was carried out with excess NBS, tribromide 8 and
tetrabromide 9 are produced. The simple NMR spectrum of
9 verifies its highly symmetric structure. Single crystals of 9′
(n-dodecyl groups are replaced by n-butyl groups) suitable for
crystallography analysis were grown from a saturated
chlorobenzene solution by slow evaporation of the solvent at
room temperature. The structure was unambiguously estab-
lished by X-ray crystallography. The molecular structure and
crystal packing of 9′ are shown in Figure 2. The bromination
sites on the perylene skeleton are at peri and bay positions.
Due to the crowdedness near the bay region, the perylene
structure of 9′ is severely twisted with much larger dihedral
angles between two naphthyl units (33.34°) than the
unbrominated analogue (19.2°).11 Like other bay-substituted
PDI derivatives (36.7° for 1,6,7,12-tetrachloro PDI13 and 40°
for 1,2,5,6,7,8,11,12-octabromo PDI14), the large twist angles
effectively block intermolecular π−π stacking and render such
molecules quite soluble in common solvents. The twist also
forces the molecule to adopt a chiral conformation. Two
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and 497 nm) exhibit slightly longer wavelength absorption
than those with bay-substituted counterparts (10 and 11 at
486 and 488 nm). All of these acceptors exhibit resembling
fluorescence (between 500 and 530 nm) with moderate Stokes
shifts (660−1230 cm−1), affirming that the nitrile group affects
the HOMO and LUMO similarly.
The LUMO energy levels of these acceptors were probed
with cyclic voltammetry. As shown in Table 1, the LUMO
levels are tuned progressively from −3.33 eV in the parent Z-
shaped PDI 3 to −4.44 eV in pentanitrile 12 with each
additional nitrile substitution. The suppression of LUMO
energy scales linearly with the number of nitrile groups.
Surprisingly, the effects of peri position and bay position nitrile
substituents are almost identical. The LUMO levels of both
trinitrile 6 and 10 are determined to be −3.99 eV, and those of
tetranitrile 7 and 11 are close to −4.20 eV. Interestingly,
reports of both Mullen and Wang demonstrated that, for the
ortho dinitirle, trinitrile, and tetranitirle PDI derivatives, the
LUMO energy levels decrease by 0.15−0.1 eV with each
substitution.15 Evidently, the peri and bay nitrile groups
stabilize the LUMO levels more effectively than their ortho
counterpart. Like most PDl-based systems, the nitrile-
substituted acceptors possess at least two reversible reductive
waves. The differences between the first and second reductive
potentials in 10−12 (∼0.3−0.5 eV) are consistently larger
than those in 5−7 (∼0.3 eV). The discrepancies presumably
reflect that the charge distributions in these systems are
confined by the distorted geometry of Z-shaped PDI.
In summary, we have synthesized Z-shaped PDI derivatives
with two to five nitrile groups. The starting building block, Z-
shaped PDI, is readily accessible through Wittig−Knoevenagel
benzannulation. After the perylene core was selectively
brominated at peri and bay positions under controlled
conditions, nitrile groups were introduced via Pd(0)-catalyzed
cyanation. Further cyanation was achieved by direct attack of
cyanide anion on the electron-deficient perylene skeleton
followed by oxidation. These soluble and stable electron-
deficient molecules potentially constitute a new class of strong
organic acceptors. With the stepwise cyanation strategy, the
LUMO levels of these acceptors are progressively lowered
from −3.33 eV to −4.44 eV. For each additional electron-
withdrawing nitrile group, the LUMO consistently decreases
by 0.2 eV independent of the cyanation sites. These acceptors
should find applications in devices like solar cells or OFETs.
Figure 2. X-ray crystal structure and packing of 9′ (chlorobenzene
molecules are removed for clarity).
enantiomeric molecules of 9′ crystallize in the achiral P2/c
space group.
The Pd(0)-catalyzed cyanation was carried out with 8 and 9
to produce trinitrile 10 and tetranitrile 11 (63% and 53%).
This robust catalytic system enables the multiple-site reactions
to produce redox-sensitive products with reasonable yields.
The fifth nitrile group was then installed at the peri position
with the nucleophilic addition/oxidation protocol to produce
12 as demonstrated in Scheme 3 (68%). Unfortunately, further
cyanation is not feasible with this strategy. Since the cyanide
anion readily attacks the peri position of 5 and 6 (Scheme 2),
the present failure cannot be attributed to a slow nucleophilic
addition. A plausible rationale is that the anion produced after
the cyanide attack becomes too stable for oxidation because it
contains five electron-withdrawing nitrile groups.
The photophysical properties of these new acceptors are
shown in Table 1. From diimide 3 to the pentanitrile diimide
Table 1. Photophysical and Electrochemical Properties of
Z-Shaped PDI 3, Z-Shaped PDI Polynitrile Derivatives (5−
7 and 10−12), and Some Linear PDI Counterparts
λmax
(nm)
PL
(nm)
LUMO
(eV)
HOMO
(eV)
Gopt
(eV)
compound
3
5
6
7
10
11
12
482
484
494
497
488
486
497
521
518
500
500
520
521
512
517
527
540
528
−3.33
−3.73
−3.99
−4.19
−3.99
−4.21
−4.44
−3.90
−4.40
−5.75
−6.13
−6.32
−6.59
−6.34
−6.59
−6.77
−6.21
−6.71
2.42
2.40
2.33
2.40
2.35
2.38
2.33
2.31
2.31
linear PDI
linear PDI−CN4
EXPERIMENTAL SECTION
(ortho)
■
linear PDI−CN2
529
−4.18
−6.44
2.26
Materials and General Procedures. All starting compounds and
reagents were purchased from commercial sources and were used
without further purification. Reaction solvents were distilled or passed
through a column of activated alumina before use. Reactions were
performed under 1 atm of dried nitrogen unless otherwise notified.
Reactions were heated with an oil bath and mixed with magnetic
stirring devices for the designated reaction intervals. The progress of
each reaction was monitored by 1H NMR or analytical thin-layer
chromatography (visualized with a 254 nm UV lamp). HPLC-grade
solvents were used for the extraction and chromatography. Flash
columns were performed with silica gel as the stationary phase. All
reported ratios of eluent solvents are based on volume. EI and FAB
mass were performed with magnetic sector analyzers. All UV−vis and
fluorescence spectra were measured in CH2Cl2 solutions (∼10−1
mM). Cyclic voltammograms were measured in CH2Cl2 solutions
(10−20 mM) with TBAPF6 as the supporting electrolyte.
(bay)
a
The UV−vis and fluorescence spectrum are measured in CH2Cl2
b
solution (∼10−1 to 10−2 mM). The cyclic voltammetry studies were
performed in dichloromethane solution (∼10−1 mM) with n-Bu4NPF6
as the supporting electrolyte. Ag/AgNO3 is the reference electrode,
and the scan rate was set to 50 mV/s. The LUMO energy levels of
electron acceptors were estimated with ferrocene (HOMO = −4.80
c
eV) as the standard. Estimated from EHOMO = ELUMO − Gopt
.
12, the bathochromic shift of absorption spectrum is merely 15
nm (482−497 nm) despite the markedly different substituents.
These results reveal that the nitrile group generally suppresses
both the HOMO and the LUMO energy levels in these
acceptors regardless of substitution sites, the number of
substituents, and substrate planarity. Closer scrutiny indicates
that substrates with peri nitrile substituents (6 and 7 at 494
1,5-Distyryl anthraquinone (1). A mixture of 1,5-diiodoantraqui-
none (1.00 g, 2.17 mmol), styrene (1.12 mL, 10.85 mmol),
(MeCN)2PdCl2 (110 mg, 0.43 mmol), tetrabutylammonium bromide
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(1.74 g, 5.42 mmol), and triethyl amine (2 mL) in dry toluene (20
mL) was heated at 100 °C under nitrogen for 24 h. The solvent was
removed in vacuo. The crude product was purified by flash
chromatography (hexane/CH2Cl2 = 1:1) to give 1 as a yellow
powdery solid (520 mg, 64%): IR (CH2Cl2, cast) ν (cm−1) 2959,
2872, 1662, 1578, 1463, 1320, 1272; 1H NMR (500 MHz, CDCl3) δ
(ppm) 8.34 (d, J = 16.3 Hz, 2H), 8.26 (d, J = 7.8 Hz, 2H), 7.96 (d, J =
7.8 Hz, 2H), 7.74 (dd, J = 7.8 Hz, 7.8 Hz, 2H), 7.63 (d, J = 7.5 Hz,
4H), 7.39 (dd, J = 7.5 Hz, 7.5 Hz, 4H), 7.30 (dd, J = 7.5 Hz, 7.5 Hz,
2H), 7.05 (d, J = 16.3 Hz, 2H); 13C {1H} NMR (100 MHz, CDCl3)
185.30, 140.31, 137.26, 136.27, 133.48, 133.12, 132.86, 129.23,
128.75, 128.56, 128.14, 127.24, 127.09; HRMS (EI) m/z [M]+ calcd
for C30H20O2 412.1463, found 412.1470.
Anthraquinone 1,5-Dicarbaldehyde (2). 1,5-Distyryl anthraqui-
none (1, 1.00 g, 2.42 mmol) was dissolved in dichloromethane (200
mL). The solution was cooled to −78 °C, and O3/O2 was bubbled
through the solution for 10 min at that temperature. The excess ozone
was then removed by bubbling nitrogen through the solution for
another 5 min. The reaction was then quenched with dimethyl sulfide
(3.0 mL). The solution was concentrated in vacuo, and the crude
product was washed with methanol (10 mL). The insoluble brown
solid was filtered to give product 2 (0.50 g, 78%). The product can be
used directly in the next step without further purification: IR
(CH2Cl2, cast) ν (cm−1) 2870, 1792, 1665, 1570, 1322, 1287, 1238,
820; 1H NMR (500 MHz, CDCl3) δ (ppm) 10.81 (s, 2H), 8.52 (dd, J
= 7.8 Hz, 1.5 Hz, 2H), 8.15 (dd, J = 7.8 Hz, 1.5 Hz, 2H), 7.94 (dd, J =
7.8 Hz, 7.8 Hz, 2 H); 13C{1H} NMR (125 MHz, CDCl3) 192.17,
183.70, 138.83, 134.59, 134.32, 134.08, 132.51, 131.55; HRMS (EI)
m/z [H]+ calcd for C16H8O4 264.0423, found 264.0430.
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone (3). N-Dodecyl-maleimide (0.62 g, 2.35 mmol) was
dissolved in dry dichloromethane (2.0 mL). The solution was cooled
to 0 °C before triethyl phosphine (1.0 M in THF, 2.0 mL, 2.00
mmol) was slowly added at the same temperature. After the mixture
was stirred for 10 min, a dichloromethane solution of 2 (0.25 g, 0.94
mmol, in 10 mL) was slowly added. The reaction was stirred at room
temperature for another 2 h before cooling to 0 °C again. DBU (360
mg, 2.35 mmol) was slowly added, and the reaction was stirred for
another 2 h at room temperature. The reaction was quenched with
cold water, and the mixture was extracted with dichloromethane (3×).
The combined organic phase was dried over MgSO4 and concentrated
in vacuo. The crude product was purified with flash chromatography
(hexane/CH2Cl2 = 3:2) to furnish diimide 3 (440 mg, 65%) as an
orange yellow powder: mp 210−211 °C; IR (CH2Cl2, cast) ν (cm−1)
2920, 2850, 1752, 1696, 1101, 802, 750; 1H NMR (500 MHz,
CDCl3) δ (ppm) 9.16 (d, J = 7.4 Hz, 2H), 8.32 (s, 2H), 8.09 (d, J =
7.4 Hz, 2H), 7.83 (dd, J = 7.4 Hz. 7.4 Hz, 2H), 3.78 (t, J = 7.6 Hz,
4H), 1.76−1.69 (m, 4H), 1.34−1.22 (m, >36H, the integration value
is inaccurate due to contamination from grease), 0.84 (t, J = 7 Hz,
6H); 13C{1H} NMR (125 MHz, CDCl3) 168.35, 167.20, 134.74,
133.31, 132.70, 132.58, 132.11, 130.49, 128.71, 128.68, 123.91,
123.17, 38.78, 31.89, 29.69, 29.61, 29.56, 29.50, 29.32, 29.23, 28.51,
27.00, 22.66, 14.08; HRMS (EI) m/z calcd for C48H58N2O4 726.4397,
found 726.4400.
6,13-Dibromo-2,9-didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-
1,3,8,10(2H,9H)-tetraone (4). To a TFA/CH2Cl2 solution of 3 (500
mg, 0.68 mmol, in 4.0 mL/2.0 mL) was added NBS (610 mg, 3.44
mmol). The reaction was stirred at room temperature for 24 h. The
reaction was quenched with a saturated solution of NaHCO3, and the
mixture was extracted with CH2Cl2 (3×). The combined organic
phase was dried over MgSO4 before evaporated in vacuo. The crude
product was purified with flash chromatography (hexane/CH2Cl2 =
3:2) to give dibromide 4 (336 mg, 56%) as an orange yellow powder:
mp 76−77 °C; IR (CH2Cl2, cast) ν (cm−1) 2923, 2853, 1762, 1706,
1400, 1363, 1121, 1075; 1H NMR (500 MHz, CDCl3) δ (ppm) 8.77
(d, J = 8.3 Hz, 2H), 8.70 (s, 2H), 8.03 (d, J = 8.3 Hz, 2H), 3.77 (t, J =
7.5 Hz, 4H), 1.72−1.70 (m, 4H), 1.34−1.22 (m, >36H, the
integration value is inaccurate due to contamination from grease),
0.84 (t, J = 7.0 Hz, 6H); 13C{1H} NMR (125 MHz, CDCl3) 167.62,
166.44, 133.32, 133.21, 133.11, 132.66, 131.73, 131.23, 127.52,
127.23, 123.60, 123.22, 38.83, 31.83, 29.54, 29.54, 29.50, 29.43, 29.26,
29.14, 28.39, 26.92, 22.59, 14.01; HRMS (EI) m/z [M + H]+ calcd
for C48H57Br2N2O4 883.2685, found 883.2698.
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone-6,13-dicarbonitrile (5). To a dioxane solution of 4
(200 mg, 0.22 mmol, in 10 mL) were added zinc cyanide (130 mg,
1.10 mmol), 1,1′-bis(diphenylphosphino)ferrocene (25 mg, 0.045
mmol), and Pd2(DBA)3 (41 mg, 0.045 mmol). The reaction mixture
was refluxed for 24 h. After cooled to room temperature, the mixture
was diluted with chloroform (20.0 mL) and filtered through Celite.
After the solvent was evaporated in vacuo, the residue was purified
with flash chromatography (hexane/CH2Cl2 = 3:2) to give dinitrile 5
(124 mg, 71%) as an orange yellow powder: mp 200−201 °C; IR
(CH2Cl2, cast) ν (cm−1) 2922, 2849, 2228, 1763, 1701, 1456, 1099,
750; 1H NMR (500 MHz, CDCl3) δ (ppm) 9.18 (d, J = 8.0 Hz, 2H),
8.81 (s, 2H), 8.22 (d, J = 8.0 Hz, 2H), 3.81 (t, J = 7.5 Hz, 4H), 1.75−
1.72 (m, 4H), 1.37−1.22 (m, 36H, the integration value is inaccurate
due to contamination from grease), 0.82 (t, J = 7.0 Hz, 6H); 13C{1H}
NMR (125 MHz, CDCl3) 167.17, 165.79, 134.37, 134.29, 132.50,
131.97, 131.70, 130.88, 126.01, 122.11, 116.22, 114.02, 39.18, 31.83,
29.63, 29.54, 29.49, 29.41, 29.26, 29.11, 28.33, 26.89, 22.61, 14.03
(only 12 signals are detected in between 110 and 170 ppm, one short
of the expected number); HRMS (EI) m/z [M + H]+ calcd for
C50H57N4O4 777.4380; found 777.4396.
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone-6,7,13-tricarbonitrile (6). To a toluene solution of
tetrabutylammonium cyanide (37 mg, 0.14 mmol, in 5.0 mL) was
added a toluene solution of 5 (100 mg, 0.12 mmol, 5.0 mL). The
reaction was stirred at room temperature for 12 h and then quenched
with acetic acid (0.1 mL) and saturated solution of K2CO3 (2.0 mL).
After the toluene was removed in vacuo, the residue was extracted
with CH2Cl2 (3×). The combined organic phase was washed with
brine, dried over MgSO4, and concentrated in vacuo. The crude
product was purified with flash chromatography (hexane/CH2Cl2 =
1:4) to give 6 (42 mg, 41%) as an orange amorphous solid: IR
(CH2Cl2, cast) ν (cm−1) 2924, 2853, 2224, 1769, 1709, 1400, 847,
750; 1H NMR (500 MHz, CDCl3) δ (ppm) 9.21 (d, J = 8.3 Hz, 1H),
9.00 (d, J = 7.5 Hz, 1H) 8,87 (s, 1H), 8.38 (d, J = 8.3 Hz, 1H), 8.27
(d, J = 7.5 Hz, 1H), 3.85−3.81 (m, 4H), 1.75−1.73 (m, 4H), 1.34−
1.22 (m, 36H, The integration value is inaccurate due to
contamination from grease.), 0.84 (t, J = 7.0 Hz, 6H); 13C{1H}
NMR (125 MHz, CDCl3) 166.85, 165.57, 165.17, 163.12, 138.94,
136.23, 134.23, 134.21, 134.19, 134.09, 133.09, 132.86, 132.47,
132.13, 131.54, 130.96, 130.04, 129.93, 127.02, 125.35, 122.62,
115.86, 115.52, 115.41, 112.00, 111.27, 104.65, 39.71, 31.83, 39.35,
31.88, 29.59, 29.53, 29.46, 29.43, 29.31, 29.14, 29.12, 28.36, 28.23,
26.94, 26.92, 22.65, 14.06; HRMS (EI) m/z [M + Na]+ calcd for
C51H55N5O4Na 824.4152, found 824.4169.
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone-6,7,13,14-tetracarbonitrile (7). To a toluene
solution of tetrabutylammonium cyanide (80 mg, 0.30 mmol, in
10.0 mL) was added a toluene solution of 5 (100 mg, 0.12 mmol, 5.0
mL). The reaction was stirred at room temperature for 12 h and then
quenched with acetic acid (0.2 mL) and saturated solution of K2CO3
(4.0 mL). After the toluene was removed in vacuo, the residue was
extracted with CH2Cl2 (3×). The combined organic phase was
washed with brine, dried over MgSO4, and concentrated in vacuo.
The crude product was purified with flash chromatography (hexane/
CH2Cl2 = 1:4) to give 7 (40 mg, 38%) as an orange amorphous solid:
IR (CH2Cl2, cast) ν (cm−1) 2924, 2853, 2224, 1772, 1711, 1460,
1400, 1099, 757; 1H NMR (500 MHz, CDCl3) δ (ppm) 9.03 (d, J =
8.0 Hz, 2H), 8.42 (d, J = 8.0 Hz, 2H), 3.85 (t, J = 7/2 Hz, 4H), 1.79−
1.72 (m, 4H), 1.36−1.22 (m, 36H, the integration value is inaccurate
due to contamination from grease), 0.84 (t, J = 6.8 Hz, 6H); 13C{1H}
NMR (125 MHz, CDCl3) 164.85, 162.96, 138.77, 136.39, 134.65,
133.29, 132.06, 130.55, 126.28, 115.04, 113.19, 111.00, 105.04, 39.84,
31.88, 29.59, 29.54, 29.45, 29.31, 29.12, 28.22, 26.93, 22.65, 14.06
(only 13 signals are detected in between 110 and 170 ppm, one short
of the expected number); HRMS (MALDI-TOF) m/z [M + Na]+
calcd for C52H54N6O4Na 849.4104, found 849.4122.
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Note
Synthesis of 4,6,13-Tribromo-2,9-didodecyl-anthra[9,1-ef:10,5-
e′f′]diisoindole-1,3,8,10(2H,9H)-tetraone (8) and 4,6,11,13-Tetra-
bromo-2,9-didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone (9). To a TFA/CH2Cl2 solution of 3 (500 mg, 0.69
mmol, in 8.0 mL/2.0 mL) was added NBS (1.20 g, 6.7 mmol, 10
equiv). The reaction was stirred at room temperature for 48 h. The
reaction was quenched with saturated solution of NaHCO3. The
mixture was extracted with CH2Cl2 (3×), and the combined organic
phase was dried over MgSO4 before concentrated in vacuo. The crude
product was then purified with flash chromatography (hexane/
CH2Cl2 = 3:2) to give tribromide 8 (145 mg, 22%) and tetrabromide
9 (240 mg, 34%) as orange powders.
2.28 mmol), 1,1′-bis(diphenylphosphino)ferrocene (16 mg, 0.029
mmol), and Pd2(DBA)3 (34 mg, 0.037 mmol). The reaction was
refluxed for 20 h before cooled back to room temperature. The
mixture was diluted with chloroform (20 mL) and the solution was
filtered through Celite. After the solvent was removed in vacuo, the
residue was purified with flash chromatography (CH2Cl2) to give 11
(84 mg, 53%) as an orange amorphous solid: IR (CH2Cl2, cast) ν
1
(cm−1) 2924, 2854, 2238, 1773, 1714, 1361, 1107, 753; H NMR
(500 MHz, CDCl3) δ (ppm) 9.02 (s, 1H) 8.57 (s, 1H) 8.46 (s, 1H),
3.91−3.78 (m, 4H), 1.77−1.66 (m, 4H), 1.41−1.22 (m, 36H, the
integration value is inaccurate due to contamination from grease),
0.85 (t, J = 7.0 Hz, 6H); 13C{1H} NMR (125 MHz, CDCl3) 165.84,
164.56, 162.30, 162.26, 140.69, 137.00, 136.39, 134.46, 134.20,
133.13, 132.23, 131.49, 131.35, 131.21, 131.10, 129.27, 127.60,
123.95, 123.61, 116.94, 116.71, 116.53, 116.17, 114.11, 113.53,
113.02, 110.26, 105.96, 40.05, 39.66, 31.89, 29.59, 29,53, 29.42, 29.40,
29.31, 29.07, 28.59, 28.51, 27.79, 22.66, 14.08; HRMS (FAB) m/z [M
+ H]+ calcd for C53H53N7O4 852.4237, found 852.4231.
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone 4,6,7,11,13-pentanitrile (12). To a toluene
solution of tetrabutylammonium cyanide (80 mg, 0.30 mmol, in 10
mL) was added a toluene solution of 11 (100 mg, 0.12 mmol, in 5
mL). The reaction was stirred at room temperature for 12 h in the
open air. After quenched by acetic acid (0.2 mL) and saturated
K2CO3 solution (4.0 mL), the solvent was removed in vacuo, and the
remaining crude product was extracted with CH2Cl2 (3×). The
combined organic phase was washed with brine, dried over MgSO4,
and concentrated. The crude product was purified with flash
chromatography (hexane/CH2Cl2 = 4:1) to give pentanitrile 12 (70
mg, 68%) as an orange amorphous solid: IR (CH2Cl2, cast) ν (cm−1)
2924, 2853, 2232, 1772, 1711, 1712, 1388, 1107, 748; 1H NMR (500
MHz, CDCl3) δ (ppm) 8.97 (s, 2H) 8.43 (s, 2H) 3.89−3.78 (m, 4H),
1.79−1.73 (m, 4H), 1.37−1.22 (m, 36H, The integration value is
inaccurate due to contamination from grease.), 0.85 (t, J = 7.0 Hz,
6H); 13C{1H} NMR (125 MHz, CDCl3) 166.10, 164.81, 136.52,
134.63, 133.95, 132.82, 131.66, 130.33, 124.60, 123.70, 117.39,
115.61, 114.87, 114.38, 39.55, 31.89, 29.60, 29.53, 29.43, 29.32, 29.10,
28.61, 26.81, 22.66; HRMS (FAB) m/z [M]+ calcd for C52H54N6O4
827.4285, found 827.4281.
Compound 8: IR (CH2Cl2, cast) ν (cm−1) 2924, 2853, 1762, 1707,
1401, 1073, 744; 1H NMR (500 MHz, CDCl3) δ (ppm) 8.80 (d, J =
8.3 Hz, 1H), 8.79 (s, 1H), 8.71 (s, 1H), 8.28 (s, 1H) 8.11 (d, J = 8.3
Hz, 1H), 3.78−3.75 (m, 4H), 1.74−1.69 (m, 4H), 1.32−1.21 (m,
36H, the integration value is inaccurate due to contamination from
grease ), 0.86−0.83 (m, 6H); 13C{1H} NMR (125 MHz, CDCl3)
167.38, 167.34, 166.92, 166.52, 138.29, 134.75, 133.78, 133.23,
132.91, 132.77, 132.41, 131.42, 130.88, 130.64, 128.83, 128.21,
127.57, 127.26, 126.36, 126.11, 125.99, 124.31, 123.62, 122.82, 39.00,
38.72, 31.89, 29.60, 29.54, 29.51, 29.47, 29.32, 29.18, 28.69, 28.39,
26.93, 26.88, 22.66, 14.08; HRMS (FAB) m/z [M − H]+ calcd for
C48H55Br3N2O4 959.1634, found 959.1632.
Compound 9: IR (CH2Cl2, cast) ν (cm−1) 2923, 2852, 1764, 1710,
1
1473, 1400, 1070, 744; H NMR (500 MHz, CDCl3) δ (ppm) 8.72
(s, 2H) 8.28 (s, 2H) 3.81−3.72 (m, 4H), 1.72−1.68 (m, 4H), 1.43−
1.22 (m, 36H, the integration value is inaccurate due to
contamination from grease), 0.85 (t, J = 7.0 Hz, 6H); 13C{1H}
NMR (125 MHz, CDCl3) 166.90, 166.69, 137.77, 134.72, 132.26,
130.31, 127.23, 126.81, 126.56, 126.42, 126.25, 123.06, 38.79, 31.89,
29.60, 29.54, 29.50, 29.31, 29.17, 28.63, 26.86, 22.66, 14.08; HRMS
(FAB) m/z [M + H]+ calcd for C48H54Br4N2O4 1039.0895, found
1039.0883.
Compound 9′. The synthetic procedure is identical with that of 9
with 2,9-dibutyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10(2H,9H)-
tetraone (3′, synthesized from 2 and n-butyl maleimide) as the
starting compound: 31% yield; IR (CH2Cl2, cast) ν (cm−1) 2931,
2957, 1765, 1711, 1401, 1362, 1076, 745; 1H NMR (500 MHz,
CDCl3) δ (ppm):8.72 (s, 2H) 8.28 (s, 2H) 3.82−3.73 (m, 4H),
1.73−1.67 (m, 4H), 1.41−1.34 (m, 4H), 0.93 (t, J = 7.5 Hz, 6H);
13C{1H} NMR (125 MHz, CDCl3) 166.90, 166.69, 137.77, 134.71,
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.1c00399.
■
sı
132.25, 130.31, 127.23, 126.81, 126.54, 126.43, 126.25, 123.06, 38.49,
30.65, 20.04, 13.62; HRMS (FAB) m/z [M + H]+ calcd for
C32H23Br4N2O4 814.8391, found 814.8384.
1H and 13C NMR spectrum for all new compounds;
UV−vis absorption, fluorescent spectrum and cyclic
voltammogram for compounds 5, 6, 7, 10, 11, and 12;
crystal structure and crystal data for compound 9′
(PDF)
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone 4,6,13-Tricarbonitrile (10). To a dioxane solution
of 8 (100 mg, 0.10 mmol, in 10 mL) was added zinc cyanide (100 mg,
0.90 mmol), 1,1′-bis(diphenylphosphino)ferrocene (11 mg, 0.02
mmol), and Pd2(DBA)3 (18 mg, 0.02 mmol). The reaction mixture
was refluxed for 24 h. After cooled back to room temperature, the
solution was diluted with chloroform and filtered through Celite. After
concentrated in vacuo, the residue was purified with flash
chromatography (hexane/CH2Cl2 = 1:4) to give trinitrile 10 (46
mg, 53%) as an orange amorphous solid: IR (CH2Cl2, cast) ν (cm−1)
2924, 2853, 2228, 1767, 1709, 1365, 1088, 748; 1H NMR (500 MHz,
CDCl3) δ (ppm) 9.24 (d, J = 7.8 Hz, 1H), 8.95 (s, 1H), 8.85 (s, 1H)
8.36 (s, 1H), 8.31 (d, J = 7.8 Hz, 1H) 3.87−3.77 (m, 4H), 1.80−1.70
(m, 4H), 1.40−1.22 (m, 36H, the integration value is inaccurate due
to contamination from grease) 0.86−0.83 (m, 6H); 13C{1H} NMR
(125 MHz, CDCl3) 166.85, 166.48, 165.46, 165.21, 136.77, 135.20,
134.97, 134.40, 134.28, 133.81, 133.13, 132.25, 132.02, 131.47,
130.47, 129.82, 129.67, 126.96, 124.86, 123.78, 123.34, 118.04,
115.88, 114.99, 114.76, 114.72, 114.01, 39.45, 39.27, 31.88, 30.90,
29.67, 29.58, 29.53, 29.44, 29.31, 29.12, 28.64, 28.31, 26.90, 26.83,
22.65, 14.08; HRMS (FAB) m/z [M + H]+ calcd for C51H56N5O4
802.4332, found 802.4330.
Accession Codes
CCDC 2061363 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
■
Chih-Hsiu Lin − Institute of Chemistry, Academia Sinica,
Taipei, Taiwan 115, Republic of China; orcid.org/0000-
0003-0492-4705; Email: chemopera@gate.sinica.edu.tw
Author
2,9-Didodecyl-anthra[9,1-ef:10,5-e′f′]diisoindole-1,3,8,10-
(2H,9H)-tetraone 4,6,11,13-Tetranitrile (11). To a dioxane solution
of 9 (200 mg, 0.19 mmol, in 10 mL) was added zinc cyanide (270 mg,
Bhargava Rao Billa − Institute of Chemistry, Academia Sinica,
Taipei, Taiwan 115, Republic of China
9825
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Note
(4) (a) Battagliarin, G.; Zhao, Y.; Li, C.; Mu
̈
llen, K. Efficient Tuning
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.1c00399
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors are grateful for the financial support from
Academia Sinica and the Ministry of Science and Technology
(Taiwan, Republic of China).
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