Difluoroboron Chelation to Quinacridonequinone: A Synthetic Method for Air-Sensitive 6,13-Dihydroxyquinacridone via Boron Complexes

Article abstract of DOI:10.1002/asia.201900219

This study aims to perform the chelation of difluoroboron (BF₂) to quinacridonequinone (QQ). The resulting dark green solid was determined to be QA-BF₂, which is a BF₂ complex of 6,13-dihydroxyquinacridone (QA-OH), and not QQ-BF₂, which is a BF₂ complex of QQ. This result indicated that QQ-BF₂ was first generated as an O,O-bidentate chelate, which immediately underwent a two-electron reduction to produce QA-BF₂. This compound was converted to air-sensitive QA-OH by undergoing hydrolysis in argon. Since QA-OH has a strong electron-donating property, it easily produced QQ via air oxidation in the solution. QA-OH also acts as a reducing reagent for quinones. The crystal packing of QA-OH is a herringbone type with short π???π contacts, and a good hole mobility has been suggested by theoretical calculations. Herein, a new synthetic method from QQ to QA-OH using BF₂ chelation and hydrolysis was proposed. QA-BF₂ and QA-OH are useful organic functional pigments and reducing reagents.

Full text of DOI:10.1002/asia.201900219

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Difluoroboron Chelation to Quinacridonequinone: A New
Synthetic Method for Air-Sensitive 6,13-Dihydroxyquinacridone
via Boron Complexes
Authors: Koichiro Moriya, Ryohei Shimada, and Katsuhiko Ono
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Difluoroboron Chelation to Quinacridonequinone: A New
Synthetic Method for Air-Sensitive 6,13-Dihydroxyquinacridone
via Boron Complexes
Koichiro Moriya, Ryohei Shimada, and Katsuhiko Ono*[a]
Abstract: This study aims to perform the chelation of difluoroboron
(
BF
was determined to be QA-BF
dihydroxyquinacridone (QA-OH), and not QQ-BF
complex of QQ. This result indicated that QQ-BF was first generated
as an O,O-bidentate chelate, which immediately underwent a two-
electron reduction to produce QA-BF . This compound was converted
2
) to quinacridonequinone (QQ). The resulting dark green solid
, which is a BF complex of 6,13-
, which is a BF
F
F
F
B
F
2
2
B
O
O
O
O
O
O
O
N
H
N
2
2
N
O
N
2
N
H
N
O
O
O
O
B
2
B
F
F
F
F
to air-sensitive QA-OH by undergoing hydrolysis in argon. Since QA-
OH has a strong electron-donating property, it easily produced QQ via
air oxidation in the solution. QA-OH also acts as a reducing reagent
for quinones. The crystal packing of QA-OH is a herringbone type with
short π···π contacts, and a good hole mobility has been suggested by
the theoretical calculations. Herein, a new synthetic method from QQ
QQ
QQ-BF2 (O,O-form)
QQ-BF2 (N,O-form)
F
F
F F
B
B
OH
O
O
O
O
O
H
N
H
N
2 2
to QA-OH using BF chelation and hydrolysis was proposed. QA-BF
N
H
N
and QA-OH are useful organic functional pigments and reducing
reagents.
H
O
OH
O
O
O
O
B
B
F
F
F F
QA-OH
QA-BF2
DHND-BF2
Organoboron complexes of β-diketonate, β-ketoiminate, and β-
diiminate and their analogs have attracted a significant amount of
attention owing to their unique fluorescence, phosphorescence,
and redox properties and polar structures.[1–6] Their fields of
application are diverse as well as boron-dipyrromethane
2
Scheme 1. Structure of BF complexes and quinacridone derivatives.
compounds, is of interest for the development of new pigments.
Prior to this study, we previously reported the structures and
[
7]
(
BODIPY). They have been applied to mechanofluorochromism,
bioimaging,[ molecular assembly, organic light-emitting diodes
8]
[9]
2 2 2
properties of DHND-BF and F-DHND-BF , which are BF
[11]
(
OLEDs),[10] solar cells, memory devices,[12] organic field-effect
complexes of 6,11-dihydroxy-5,12-naphthacenedione (DHND)
and its perfluoro derivative (F-DHND).[5a,b] These compounds
exhibit n-type semiconductor performance in OFETs owing to
their high electron affinities.
[
13]
[14]
[15]
transistors (OFETs),
other external stimuli.[ The functionalization with organoboron
and sensing for oxygen,
ions,
and
16]
chelation primarily involves modifying or enhancing the ligand
performance. Furthermore, recent studies have utilized the BF
2
The BF
2
chelation of QQ produced a dark green solid. This
complex as a reaction catalyst or substance.[ These complexes
17]
was predicted to be either of the two geometric isomers of QQ-
are useful for the synthetic reactions of new compounds.
BF
BF
2
(the O,O- or N,O-bidentate chelate form); however, it was a
complex of 6,13-dihydroxyquinacridone (QA-OH) and was
On the contrary, quinacridone (QA) derivatives are synthetic
pigments that have a vivid color and weather resistance and are
used in various industrial applications.[ They exhibit red to
purple color in the solid state but exhibit yellowish color in solution.
This change in color in the solid state arises from intermolecular
2
determined as QA-BF
chelate of QA-BF
sensitive QA-OH was obtained as a dark purple solid.[ To the
best of our knowledge, this conversion from QQ to QA-OH is the
first example of a synthetic method based on the electron affinity
of the BF
functional dyes and pigments. Herein, we report the structures,
reactions, and properties of QA-BF and QA-OH.
The BF chelation was performed by heating a mixture of QQ
and boron trifluoride diethyl etherate (BF ·OEt ) at reflux to
2
(Scheme 1). Furthermore, when the boron
18]
2
was removed via hydrolysis in argon, air-
22]
interactions via hydrogen bonds. They have also been
investigated as emitters in OLEDs[
19]
and as p-type
2
complex, and it is useful for the development of new
[20]
[21]
semiconductors in OFETs or organic photovoltaics (OPVs).
Since QA is one of the important components in industrial organic
2
pigments,
the
difluoroboron
(BF
2
)
chelation
of
2
quinacridonequinone (QQ), which is a member of the QA group
3
2
produce a dark green solid (Supporting Information). This
compound is stable in air in the solid state (M.p. > 300 °C) but
unstable in solution because it undergoes hydrolysis. However, it
was possible to obtain the H NMR spectrum of the product by
6
promptly measuring it in [D ]DMSO (Figure S1 in the Supporting
[
a]
K. Moriya, R. Shimada, Prof. Dr. K. Ono
Graduate School of Engineering
Nagoya Institute of Technology
Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
E-mail: ono.katsuhiko@nitech.ac.jp
1
Information). In a magnetic field ranging from 7 to 9 ppm, four
signals that were assigned to aromatic protons were observed. A
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found
1
broad signal was also found at 14.1 ppm. Since the H NMR
under:https://doi.org/10.1002/
spectrum showed a decrease in the signal after adding a drop of
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O
O
D
2
O to the solution, the broad signal was assigned to an NH or
OH proton. This result indicated that the product was neither the
O,O-form nor the N,O-form of QQ-BF . Additionally, a yellow solid
1
.356(4)
1.217(2)
1
.389(5)
1.400(6)
1.377(8)
1.481(2)
2
of QQ gradually precipitated upon standing the solution in air.
X-ray crystallography was performed to determine the
molecular structure of the dark green solid. A single crystal was
obtained by slowly cooling the hot anhydrous DMF solution of the
1.417(5)
1.416(6)
1.398(2)
[
23]
1
.391(5)
1.487(2)
solid. The molecular structure was determined to be QA-BF
Figure 1A). The bond lengths in the central six-membered ring
were compared with those of QA and anthraquinone (AQ),[ as
shown in Figure 2. The six-membered ring is not a quinone form
similar to AQ but an aromatic form similar to QA. Furthermore, the
C–O single bond length is 1.356(4) Å, which is longer than
2
O
QA-BF2
O
(
QA
AQ
24]
2
Figure 2. Bond lengths [Å] in the central six-membered rings of QA-BF , QA,
and AQ as measured via X-ray crystallography. These rings are
centrosymmetric.
1
.217(2) Å for the C–O double bond in AQ. Thus, the product was
determined to be QA-BF The molecular structure is
centrosymmetric, and the quinacridone moiety is nearly planar.
This crystal contains two DMF molecules per QA-BF molecule.
The QA-BF molecules stack along the a axis (Figure 1B), and
2
.
The UV/Vis spectrum of the dark green solid in DMSO showed
long-wavelength absorptions with maxima at 688 and 743 nm (sh),
and a short-wavelength absorption with a maxima at 318 nm
2
2
(
2 2
Figure 3A). The spectra of QA-BF and QQ-BF (O,O-form) were
short F···C contacts [3.089(5) Å] were observed. This contact
distance is shorter than the sum of the van der Waals radii of the
fluorine and carbon atoms (3.17 Å). Since the molecular stacking
is governed by these short contacts, the π···π overlap region
between quinacridone moieties is small (Figure 1C). Moreover,
the molecules form a tape-like structure with short F···H-C
contacts (Figure 1D). The contact distance between the F and H
atoms is 2.401 Å, which is shorter than the sum of their van der
Waals radii (2.67 Å). These molecular arrangements are similar
simulated by time-dependent density functional theory (TDDFT)
calculations at the B3LYP/6-31G(d) level,[25] which are shown in
Figures 3B and 3C, respectively. The long-wavelength excitation
energies (oscillator strengths) of QA-BF
0.079) and 527 nm (0.64), respectively. The experimental
spectrum agreed well with the simulated spectrum of QA-BF
Thus, the dark green solid was conclusively determined to be QA-
BF . To investigate the electron affinity of QA-BF , cyclic
voltammetry (CV) experiments were performed in a DMSO
solution with 0.1 M nBu NClO . The voltammogram showed two
reversible reduction waves and one irreversible oxidation wave
Figure S2 in the Supporting Information). The
2 2
and QQ-BF are 681
(
2
.
2
2
.[5b]
to those found in the crystal of F-DHND-BF
2
4
4
(
Figure 3. UV/Vis spectra. A) Measurement in DMSO solution. Simulations of B)
QA-BF and C) QQ-BF (O,O-form) calculated using TDDFT at the B3LYP/6-
1G(d) level.
2
Figure 1. Crystal structure of QA-BF : A) molecular structure drawn at the 50%
probability level (ORTEP), B) molecular stacking, C) overlap mode, and D)
molecular tape.
2
2
3
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half-wave reduction potentials (Ered) of QA-BF
2
were observed at
+
−1.00 and −1.44 V versus Fc/Fc . Therefore, the electron affinity
of QA-BF
2
is slightly higher than that of QQ (Ered: −1.15 V) but
(Ered: −0.33 and −0.81 V).
Furthermore, the peak oxidation potential (E
ox) was observed at
0.38 V, and QA-BF showed a strong electron-donating ability.
This suggested that QQ-BF has a high electron affinity.
Based on the above experimental data, we determined that
QA-BF was obatined as a dark green solid via the reaction of QQ
with BF ·OEt . This indicated that QQ-BF was first generated and
immediately underwent a two-electron reduction to form QA-BF
although the electron source has not been specified. When the
green solution of QA-BF was hydrolyzed in air, a yellow solution
of QQ was obtained. Scheme 2 illustrates the outline of these
reactions. The hydrolysis of QA-BF in argon provided a dark blue
much lower than that of DHND-BF
2
p
+
2
2
2
3
2
2
2
,
2
2
solution of QA-OH, indicating that QQ was generated via air
oxidation of QA-OH. To investigate the hydrolysis reaction from
Figure 4. 1H NMR (400 MHz) spectra of the mixture of QA-BF
benzoquinone (1:1 molar ratio) in [D ]DMSO containing 4 vol% of water in
argon: A) immediately after beginning the reaction and B) after 24 h. These
spectra indicate the reduction of benzoquinone to hydroquinone by QA-OH
generated in the hydrolysis of QA-BF . No peaks attributed to QQ were
2
observed at the end of the reaction because QQ precipitated because of its poor
solubility.
and
2
1
QA-BF
QA-BF
2
to QA-OH in detail, time-dependent H NMR spectra of
6
2
in [D
6
]DMSO containing 4 vol% of H
2
O in argon were
measured. These spectra and abundance ratio of compounds are
shown in Figures S3 and S4 (in the Supporting Information),
respectively. After 1 h of the reaction, the monoBF
5%, and within 4 h, QA-BF disappeared. After 5 h, the ratio of
QA-OH reached 80%, and after 8 h, it ranged between 90% and
6%. The conversion ratio from QA-BF to QA-OH depended
2
ratio reached
4
2
9
2
showed an irreversible oxidation wave and reversible reduction
wave (Figure S7 in the Supporting Information). The peak
upon the amount of water in the DMSO, and the hydrolysis
quantitatively proceeded when using 5 vol% or more water at
room temperature. QA-OH was stable in solution in argon.
However, when the solution was left in air, QQ precipitated. When
the hydrolysis of QA-BF was performed in the presence of
2
equimolar benzoquinone, hydroquinone was produced, as shown
in Figure 4. The other available quinones are in Figure S5
+
oxidation potential was −0.09 V versus Fc/Fc , and QA-OH had a
sufficient electron-donating ability to cause air oxidation. The half-
wave reduction potential was −1.69 V, which was negatively
shifted from that of QA-BF
Figure 5 shows the energy diagram of the HOMOs and
LUMOs of QA-BF and its related compounds obtained via DFT
calculations at the B3LYP/6-31G(d) level. Because QA-BF is a
reduced form of QQ-BF , the HOMO and LUMO energies of QA-
BF are higher than those of QQ-BF , respectively. The LUMO
energy of QA-BF is higher than that of DHND-BF (−3.76 eV),
and the LUMO energy of QQ-BF is much lower that of DHND-
BF . Furthermore, the HOMO and LUMO energies increase in the
2
(−1.00 V).
2
(
Supporting Information).
2
In the UV/Vis spectrum of QA-OH in DMSO, characteristic
2
absorption bands with a maxima at 577 and 605 nm were
observed (Figure S6 in the Supporting Information). According to
the TDDFT calculations, the corresponding excitation energy
2
2
2
2
2
(
oscillator strength) was 557 nm (0.087), which supports the
2
molecular structure. The CV experiments of QA-OH in DMSO
order of QA-BF
2
2
, monoBF , and QA-OH, and the HOMO-LUMO
F
F
F F
B
B
O
O
O
O
O
O
H
N
H
N
BF3·OEt2
[Red]
N
O
N
H
N
N
H
O
O
O
O
O
B
B
QQ
F
F
QQ-BF2
F
F
QA-BF2
F
F
B
OH
OH
O
O
O
H
N
H
N
[
Ox]
H2O
H2O
N
H
N
H
O
O
OH
QA-OH
monoBF2
2 2
Scheme 2. Formation of QA-BF from QQ and regeneration of QQ via monoBF and QA-OH.
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2
Figure 5. HOMO and LUMO energies [eV] of QA-BF and its related compounds
calculated via DFT at the B3LYP/6-31G(d) level.
energy. This indicates that the electronic properties depend on
the number of boron chelates. The space arrangements of HOMO
and LUMO are similar among these compounds and are
delocalized on the whole quinacridone moiety (Figure S8 in the
Supporting Information). This theoretical energy diagram
supported the nature of the BF
UV/Vis spectra and CV experiments.
QA-OH was obtained as a dark purple solid from a solution of
QA-BF in DMSO containing 5 vol% of water at 90 °C in argon
Supporting Information). We also succeeded in obtaining a dark
blue single crystal (M.p. 293–294 °C) suitable for X-ray
2
complexes observed in the
2
(
[
23]
crystallography. Since it was a good crystal with R
1
= 0.049 [I >
2σ(I)], all hydrogen atoms were determined from the difference
Fourier map and were refined. The molecular structure is
centrosymmetric and planar (Figure 6A), and the bond lengths in
the central six-membered ring are almost the same to those as
Figure 6. Crystal structure of QA-OH: A) molecular structure drawn at the 50%
probability level (ORTEP), B) bond lengths [Å] in the central six-membered ring,
C) hydrogen bonds with DMSO molecules, and D) the herringbone structure.
QA-BF
C–C distances are 1.395(3), 1.408(3), and 1.413(3) Å. In the
(1H)-pyridone moieties, the C–O double bond is 1.256(2) Å. The
2
(Figure 6B). The C–O single bond is 1.351(2) Å, and the
4
argon. Although QA-OH is air sensitive owing to its strong
electron-donating ability, we succeeded in obtaining it as a dark
purple solid. Therefore, the BF chelation of QQ is a new and
2
convenient synthetic method for deriving from QQ to QA-OH.
Moreover, QQ was regenerated by air oxidation of QA-OH in
solution. QA-OH also behaved as a reducing reagent, e.g.,
converting benzoquinone to hydroquinone. Since QA-OH can be
crystal contains two DMSO molecules per QA-OH molecule, and
QA-OH is surrounded by six DMSO molecules (Figure 6C). The
DMSO molecules are in contact with OH, CO, and NH moieties of
QA-OH via hydrogen bonds. Therefore, QA-OH was found to be
stable in air in the solid state despite easy air oxidation in solution.
The QA-OH molecules stacked with an average interplanar
distance of 3.29 Å, forming a herringbone structure along the b
axis (Figure 6D). The herringbone angle is 82°. This packing
structure is characterized by a stacking pair and edge-to-edge
pairs, as shown in Table S1 (Supporting Information). The value
of electronic coupling for hole transfer was calculated to be 48 and
2
easily generated upon the hydrolysis of a QA-BF solution, it may
be used as an organic reducing reagent and oxygen sensor.
These compounds are also applicable to organoelectronics as
functional pigments because they have characteristic absorptions
of green or blue color.
5
meV for the stacking and edge-to-edge pairs, respectively. The
reorientation energy was determined to be 319 meV. From these
2
−1
−1
values, a hole mobility of 0.05 cm
V
s
was theoretically
Acknowledgements
obtained. This value was slightly lower than the experimental and
2
−1 −1 [20a]
theoretical values of QA (0.2 cm V s ).
In conclusion, we studied
quinacridonequinone (QQ). Since the generated BF
This work was supported by JSPS KAKENHI Grant Number
JP15K05422. We thank Prof. Dr. Hidehiro Uekusa (Tokyo
Institute of Technology) and Dr. Masaaki Tomura (Institute for
Molecular Science) for their advice on the X-ray crystallographic
studies. We also thank Prof. Dr. Motonori Watanabe (Kyushu
University) for his advice on the mobility calculations. The DFT
BF
2
chelation
to
2
complex
(
(
QQ-BF
QA-BF
2
) possesses a strong electron affinity, its reduced form
) is produced as a dark green solid. This compound is
2
stable in the solid state, whereas it underwent hydrolysis in
solution to produce 6,13-dihydroxyquinacridone (QA-OH) in
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Chemistry - An Asian Journal
10.1002/asia.201900219
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Redox Chemistry
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K. Moriya, R. Shimada, K. Ono*
Page No. – Page No.
Difluoroboron Chelation to
Quinacridonequinone: A New
Synthetic Method for Air-Sensitive
6
,13-Dihydroxyquinacridone via
BF
green solid was a BF
determined to be QA-BF
2
chelation to quinacridonequinone (QQ) was performed. The resulting dark
complex of 6,13-dihydroxyquinacridone (QA-OH) and was
. This compound underwent hydrolysis in argon to
Boron Complexes
2
2
produce QA-OH as a dark purple solid. Furthermore, QA-OH was converted to QQ
by air oxidation or in the presence of benzoquinone. In this study, a new synthetic
method from QQ to QA-OH via BF
2
complexes was found.
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