Color-tunable arylaminoanthraquinone dyes through hydrogen-bond-assisted charge transfer interaction

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Color-tunable arylaminoanthraquinone dyes

through hydrogen-bond-assisted charge transfer

Cite this: RSC Adv., 2021, 11, 24217

interaction†

ab

Yotaro Kasahara^band Tomoyuki Akutagawa

*

Takashi Takeda,

We prepared a series of arylaminoanthraquinone derivatives, including those with electron-accepting

sulfone units and/or with electron-donating dialkylamino units. A color-tunable anthraquinone library

that reached into the NIR region could be prepared through the precise control of frontier orbitals. Fine

color-tuning was achieved through proper selection and positioning of the substituents. Eﬀective

intramolecular hydrogen-bond-assisted charge transfer interaction between electron-donating aniline/

Received 22nd May 2021

Accepted 5th July 2021

p-phenylenediamine and electron-accepting anthraquinone substructures induced

a signiﬁcant

DOI: 10.1039/d1ra03985g

bathochromic shift of anthraquinone. The number and position of the substituents and the molecular

rsc.li/rsc-advances

conformation also signiﬁcantly contributed to determining photophysical properties.

especially used for this purpose because of their strong electron-

accepting properties.¹Especially, anthraquinone has been used

due to its easy functionalization.⁵¹Several commercially avail-

Introduction

Recently, p-conjugated molecules with a small HOMO–LUMO

gap that absorb long-wavelength light, including near-infrared

(NIR) light have attracted attention^1–6due to their potential

for use in optoelectronic devices,^5,7–11optical devices,^1,6,12and

medical applications.^13–15There are several approaches to

develop such molecules, including the expansion of p-conju-

gation and the introduction of an open-shell biradical unit in p-

conjugation. A variety of long-wavelength absorbing dyes have

been developed with these strategies, including porphyrin/

phthalocyanine derivatives,¹including their conjugated

able dyes have an anthraquinone skeleton, such as the disperse

blues. Some disperse blues contain electron-donating aniline/p-

phenylenediamine unit(s) fused with an electron-accepting

anthraquinone core. Since the degree of intramolecular CT

interaction can be modulated through the electron-donating/

accepting properties of D and A, this skeleton could serve as

a color-tunable long-wavelength absorbing dye. However, little

is known about long-wavelength absorbing dyes based on

a aminoanthraquinone scaﬀold.

We previously studied the photophysical and electro-

chemical properties of arylsulfonamide-substituted anthraqui-

nones 3, 9, 14, and 20.^52,53Thanks to eﬀective intramolecular N–

H/O]C hydrogen bonds at the peri-position of anthraquinone

through xation of the conformation by bulky terminal

substituents, the electron-accepting properties of the anthra-

quinone units signicantly increased, which induced a signi-

cant bathochromic shi in UV-Vis spectra thanks to hydrogen-

bond-assisted CT interaction (Fig. 1a).⁵⁴We also revealed that N-

methylation of these derivatives induced a drastic change in

conformation to completely suppress this intramolecular CT

interaction.⁵⁵

array,^16–19

polymethine/cyanine

derivatives,^1,20–25

boron-

dipyrromethene (BODIPY) derivatives,^26,27polyacenes,^28–31zeth-

renes derivatives,^32–35and indenouorene derivatives.^36–47

However, these compounds oen suﬀer from diﬃcult synthesis

and low solubility in common organic solvents.

The introduction of intramolecular charge transfer (CT)

interaction between an electron-donating group (D) and an

electron-accepting group (A) in a p conjugated unit is also

widely used to develop long-wavelength absorbing dyes.^{1–4,48–50}

While a variety of long-wavelength absorbing dyes have been

developed, quinone and its p-extended derivatives have been

In this work, we systematically prepared arylaminoan-

thraquinones and investigated their photophysical and elec-

trochemical properties (Fig. 1b). Thanks to hydrogen-bond-

assisted CT interaction, these compounds showed signicant

bathochromic absorption compared to anthraquinone. Their

photophysical properties could be systematically modulated by

the introduction of electron-donating dialkylamino groups at

peripheral phenyl groups or the insertion of electron-accepting

sulfone groups between an amino unit and phenyl group. As

^aInstitute of Multidisciplinary Research for Advanced Materials, Tohoku University,

Katahira 2-1-1, Aoba-ku, Sendai, 980-8577, Japan. E-mail: takashi@tohoku.ac.jp

^bDepartment of Applied Chemistry, Graduate School of Engineering, Tohoku

University, Sendai, Miyagi 980-8579, Japan

† Electronic supplementary information (ESI) available: ORTEP drawing of 22.

Cyclic voltammograms of 1–23 classied according to the substituent. HOMO

and LUMO of 1–6, 11, 13–23. Copies of the ¹H and ¹³C NMR spectra of new

compounds. Cartesian coordinates for the optimized structures of 1–23. CCDC

2063387. For ESI and crystallographic data in CIF or other electronic format see

DOI: 10.1039/d1ra03985g

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Fig. 1 (a) Hydrogen-bond-assisted CT interaction in aminoanthraquinone derivatives with bulky aryl substituents.⁵²(b) Chemical structure of

aminoanthraquinones described in this manuscript.

a result, color-tunable aminoanthraquinone dyes that reached The reaction of alkylphenylamine and alkylphenylsulfonamide

into the NIR region could be prepared.

without terminal electron-donating alkylamino groups proceeded

smoothly to give the corresponding arylamino derivatives (1, 13,

19)^58,59and arylsulfonamide derivatives (3, 9, 14, 20) in good yields.

In the case of 1,5-disubstituted (13, 14) and 1,4,5,8-tetrasub-

stituted derivatives (19, 20), a terminal tert-butyl group was

necessary to increase the solubility to accomplish the reaction. In

the reactions of 1,4- and 1,8-dichloroanthraquinone with stronger

electron-donating N,N-dimethyl-1,4-phenylenediamine, the reac-

tion did not proceed completely and gave both the desired

disubstituted derivatives (2, 8) and monosubstituted derivatives

with unreacted chlorine atom (5, 11). If we consider that a signif-

icant amount of unreacted monochloro derivative was recovered

only in the reaction with phenylenediamine derivatives, this could

be accounted for by suppression of the reactivity of monochloro

intermediate with Pd catalyst due to the decreased electron-

withdrawing properties of arylanthraquinones by introduction

of an electron-donating dimethylaminophenyl unit. In the reac-

tion of 1,5-dichloroanthraquinone, only monosubstituted deriva-

tive (16) was obtained, due to the relatively limited solubility of

1,5-disubstituted derivatives (see above), in addition to limited

reactivity. In the reaction with N,N-dimethylaminophenylsulfo-

namide,⁶⁵only the corresponding 1,4- and 1,8-substituted deriv-

atives 4, 10 were obtained in moderate yields, whereas the 1,5- and

1,4,5,8-substituted derivatives were not obtained under the same

reaction conditions. If we consider the decreased electron-

donating nature of the terminal NH₂group suitable for the

Buchwald–Hartwig cross-coupling reaction due to the neigh-

boring electron-accepting sulfone unit, this limited reactivity was

due to the limited solubility of these derivatives, rather than the

reactivity. To obtain 1,5- and 1,4,5,8-substituted derivatives, we

planned to introduce long alkyl chains (butyl groups for 15 and

Results and discussion

Preparation of aminoanthraquinones with electron-donating/

accepting units

We prepared a series of aminoanthraquinones with diﬀerent

electron-donating/accepting units. Fig. 1 shows the molecular

structures of aminoanthraquinones described in this manu-

script. Since our previous study revealed that a bulky aryl

substituent at the peripheral position of aminoanthraquinones

worked eﬀectively to form N–H/O]C hydrogen bonds, we

adopted this strategy to maximize hydrogen-bond-assisted CT

interaction. We selected a dialkylamino unit on terminal phenyl

groups as an electron-donating unit and a sulfone unit between

aminoanthraquinone and terminal phenyl group as an electron-

accepting unit. The positional and numerical eﬀects of

substituents on the photophysical and electrochemical prop-

erties should also be considered, since phenylenediamine and

its derivatives have been reported to be strong electron donors.

Based on this strategy, we synthesized 23 kinds of amino-

anthraquinones for this purpose, including those we previously

reported^52,55and those in the literature (1, 7, 13, 19).^56–59

A

substituent was introduced at the 1,4-, 1,5-, 1,8- or 1,4,5,8-

positions in each compound. Terminal methyl, butyl, tert-butyl

and hexyl groups were introduced to improve their solubility.

Fig. 2 summarizes the synthesis of 1–23 with/without electron-

donating/accepting units. Most of the compounds were synthe-

sized through a Buchwald–Hartwig cross-coupling reaction^60–63or

Ullmann coupling reaction⁶⁴between the corresponding chlor-

oanthraquinone and arylamine/arylsulfonamide, respectively.

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Fig. 2 Synthesis of 1–23.

hexyl groups for 21) to a terminal amino group, instead of structure of 22 was rigorously characterized by single-crystal X-ray

a methyl group. To achieve this, we changed the synthetic strategy structural analysis (Fig. S1 in ESI†). N-Methylation of arylsulfo-

and planned to react the corresponding aminoanthraquinone namide derivatives 3, 9, 14, 20 gave the corresponding N-meth-

with 4-(dialkylamino)benzene sulfonyl chloride. 4-(Dibutylamino) ylated derivatives (6, 12, 18, 23). All newly synthesized compounds

benzenesulfonyl chloride and (dihexylamino)benzenesulfonyl were characterized by ¹H and ¹³C NMR, IR and HR-MS spectros-

chloride were newly prepared from dibutylamine and dihexyl- copy and elemental analyses.

amine, respectively, by the reaction with (TMSO)₂SO₂followed by

PCl₅. The reaction of the corresponding commercially available

Photophysical properties

aminoanthraquinone with 4-(dialkylamino)benzene sulfonyl

chloride in pyridine proceeded smoothly to give the desired

dialkylaminophenylsulfonamide-substituted anthraquinones 15

and 21. When we tried the reaction between (dibutylamino)ben-

zenesulfonyl chloride and 1,4,5,8-tetraaminoanthraquinone,

prepared in-house by hydrolysis of 20, we unexpectedly obtained

partly reacted 1,4-disubstituted-5,8-diaminoanthraquinone 22,

although we could not clarify the mechanism or selectivity. The

We measured UV-Vis/NIR spectra of 1–23 to investigate the

eﬀect of the electron-donating/accepting substituent and the

positional/numerical eﬀects of the substituents. Fig. 3 and 4

show the UV-Vis spectra in CH₂Cl₂classied according to the

substitution position and the substituent, respectively, and

Table 1 summarizes the photophysical and electrochemical

properties of 1–23, in addition to their theoretical HOMO and

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Fig. 3 UV-Vis spectra of 1–23 in CH₂Cl₂classiﬁed according to the substitution position. The color was determined by the introduced

substituent. The dotted line indicates monochloro-monosubstituted derivatives or diamino-disubstituted derivative.

Fig. 4 UV-Vis spectra of 1–22 in CH₂Cl₂classiﬁed according to the substituent. The color was determined by the position of the introduced

substituent. The dotted line indicates monochloro-monosubstituted derivatives or diamino-disubstituted derivative.

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Table 1 Photophysical and electrochemical properties, calculated HOMO–LUMO energy and the lowest-energy absorption peak

3^b

l_end

E_pa

E_pc

HOMO^e

LUMO^e

Abs. calc.^f

a

c

d

Compd

l_max

1

2

3

4

5

6

7

8

559

576

434

442

534

331

645

652

468

494

529

337

539

432

530

418

333

758

539

568

626

355

11 800

10 700

10 200

7200

5000

2800

15 000

13 900

6800

654

755

498

535

707

403

718

795

547

592

693

410

646

494

547

721

498

400

855

624

686

677

431

1.61^h

0.83^h

NA^k

ꢀ0.92,ⁱꢀ1.27ⁱ

ꢀ0.98,ⁱꢀ1.37ⁱ

ꢀ0.52,ⁱꢀ0.92ⁱ

ꢀ0.55,ⁱꢀ0.94ⁱ

ꢀ0.87,ⁱꢀ1.25ⁱ

ꢀ0.87,ⁱꢀ1.36ⁱ

ꢀ0.95,ⁱꢀ1.28ⁱ

ꢀ1.00,ⁱꢀ1.30ⁱ

ꢀ0.60ⁱ

ꢀ5.19

ꢀ4.65

ꢀ6.41

ꢀ5.75

ꢀ4.93

ꢀ6.30

ꢀ4.82

ꢀ4.36

ꢀ6.09

ꢀ5.53

ꢀ5.02

ꢀ6.33

ꢀ5.25

ꢀ6.44

ꢀ5.67

ꢀ4.96

ꢀ5.74

ꢀ2.82

ꢀ4.40

ꢀ5.96

ꢀ5.44

ꢀ5.05

ꢀ6.20

ꢀ2.59

ꢀ2.33

ꢀ3.15

ꢀ2.91

ꢀ2.64

ꢀ2.72

ꢀ2.54

ꢀ2.25

ꢀ3.18

ꢀ2.91

ꢀ2.62

ꢀ2.74

ꢀ2.59

ꢀ3.15

ꢀ2.95

ꢀ2.64

ꢀ2.98

ꢀ6.28

ꢀ2.44

ꢀ3.37

ꢀ2.98

ꢀ2.61

ꢀ2.62

577

651

463

512

651

472^l

609

659

495

557

615

481^l

555

449

534^l

634

526^l

495^l

726

563

593

573

480^l

1.43^h

0.73ⁱ

NA^k

1.01, 1.46ⁱ

0.77^h,j

NA^k

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

6600

1.42^h

0.77^h

NA^k

ꢀ0.52,ⁱꢀ0.65ⁱ

ꢀ0.87,ⁱꢀ1.28ⁱ

ꢀ0.82,ⁱꢀ1.29ⁱ

ꢀ0.89,ⁱꢀ1.26ⁱ

ꢀ0.53ⁱ

5400

3100^g

15 200

9800

1.40^h

NA^k

7900

1.46ⁱ

ꢀ0.61ⁱ

7700

0.77ⁱ

ꢀ0.87,ⁱꢀ1.30ⁱ

ꢀ0.64,ⁱꢀ0.91ⁱ

ꢀ0.83,ⁱꢀ1.36ⁱ

ꢀ0.97,ⁱꢀ1.22ⁱ

ꢀ0.21,ⁱꢀ0.54ⁱ

ꢀ0.35,ⁱꢀ0.66ⁱ

ꢀ0.89^i,j

3900^g

3400

1.24^h

NA^k

27 900

15 100

13 700

32 700

2800^g

0.60,ⁱ1.02^h

NA^k

1.46^h

0.97,ⁱ1.38^h

NA^k

ꢀ0.92,ⁱꢀ1.51ⁱ

a

b

c

d

e

nm. Measured in CH₂Cl₂. M^ꢀ1cm^ꢀ1

.

nm. Shortest wavelength with 3 < 500. V vs. Ag/AgCl. Measured in CH₂Cl₂containing Bu₄_gNBF₄. eV.

f

Calculated at the B3LYP/6-31G(d) level. Theoretical HOMO–LUMO transition energy in nm. Calculated at the B3LYP/cc-pVDZ level. Shoulder.

h

j

Irreversible. ⁱReversible. Broad. ^kNot observed. ^lForbidden transition (oscillator strength < 0.05).

LUMO energies and the lowest-energy absorption peak. As seen energy (1: ꢀ5.19 eV; 3: ꢀ6.41 eV) than that in LUMO energy (1:

in the UV-Vis spectra and Fig. 5, we could prepare a color- ꢀ2.59 eV; 3: ꢀ3.15 eV) (Table 1). Substitution of a terminal alkyl

tunable anthraquinone library through precise control of the group with an electron-donating dialkylamino unit also aﬀected

frontier orbital. Fine color-tuning was achieved through proper the optical properties, which was suitable for ne tuning.

selection and positioning of the substituents. As shown in Substitution of the terminal methyl groups of 1 and 3 with

Fig. 3, the photophysical properties of aminoanthraquinone dimethylamino groups (2 and 4, respectively) induced a slight

could be greatly modulated by selecting the substituents. In the red shi of the absorption peak (l_max: 17 and 10 nm, respec-

case of 1,8-disubstituted anthraquinones, that with a tolyla- tively) and a moderate-to-large red shi of the absorption end

mino group (1) showed bathochromic absorption at l_max(l_end: 95 and 37 nm, respectively). This red shi is accounted for

559 nm, which is red-shied by 233 nm compared to that for by a increase in the HOMO energy (1: ꢀ5.19 eV; 2: ꢀ4.65 eV/3:

anthraquinone. This could be accounted for by eﬀective intra- ꢀ6.41 eV; 4: ꢀ5.75 eV, Table 1). A similar tendency of the

molecular CT interaction between the electron-donating substituent eﬀect was observed for other positional isomers.

aniline/p-phenylenediamine substructure and the electron- Halogen substituents also signicantly contributed to deter-

accepting anthraquinone substructure (see below). Introduc- mine the photophysical properties. For example, mono-

tion of an electron-accepting sulfone unit between amino and substituted derivatives 5, 11, and 16 with dialkylphenylamino

aryl units signicantly modulated the photophysical properties. groups showed a hypochromic shi of ca. 40 nm compared to 2

Tolylsulfonamide-substituted anthraquinone

3 showed an with the same aniline substructure. While arylsulfonamide

absorption peak at 434 nm, which is blue-shied by 125 nm derivatives (3, 9, 14, 20) showed unique uorescence even with

compared to that of 1, due to a larger decrease in the HOMO

Fig. 5 Photographic demonstration of ﬁne color-tuning with aminoanthraquinone-based dyes with 1–23 (arranged by compound number from

the left).

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Fig. 6 Cyclic voltammograms of 1–23 measured in CH₂Cl₂classiﬁed according to the substitution position. The color was determined by the

introduced substituent. The dotted line indicates monochloro-monosubstituted derivatives or diamino-disubstituted derivative.

a non-uorescent anthraquinone core,⁵²other derivatives did alkylphenylamino groups showed a large red shi of ca. 110 nm

not exhibit uorescence.

compared to that of the corresponding 1,4-disubstituted 7 with

In addition to the kinds of substituents, the position and the same p-phenylenediamine electron-donating groups. DFT

number of the substituents also signicantly aﬀected the pho- calculation indicates that the orbital degeneracy of electron-

tophysical properties of these derivatives, as summarized in donating substructure units contributed to increase the

Fig. 4. The absorption peak/end were signicantly diﬀerent for HOMO energy (19: ꢀ4.40 eV, 7: ꢀ4.82 eV, Fig. S6†). As a result,

positional isomers with the same substituents. For example, for signicant red shi occurred in tetrasubstituted derivatives.

alkylphenylamino derivatives (1, 7, 13, 19), the absorption peak

In addition, N-methylation induced a drastic hypochromic

diﬀers by ca. 220 nm (13: 539 nm, 19: 758 nm). This large shi due to the change in the conformation of a terminal

diﬀerence in photophysical properties could be understood in arylamino/arylsulfonamide group.⁵⁵For example, the absorp-

terms of the diﬀerent electron-donating natures of the aniline/ tion peak at the longest wavelength for N-methylated tetrasub-

p-phenylenediamine substructure. HOMO energies of 7 (ꢀ4.82 stituted derivative 23 showed a blue shi of 190 nm compared

eV) and 19 (ꢀ4.40 eV) with stronger electron-donating p-phe- to that of the corresponding N–H derivative 20. N-Methylation at

nylenediamine substructure are higher than those of 1 (ꢀ5.19 the congested peri-position of the anthraquinone unit induced

eV) and 13 (ꢀ5.25 eV) with weaker electron-donating aniline a drastic change in conformation from a coplanar arrangement

substructure. The 1,4-disubstituted and 1,4,5,8-tetrasubstituted to an orthogonal arrangement between the anthraquinone

derivatives with a stronger electron-donating p-phenylenedi- scaﬀold and arylsulfonamide substituents. This drastic struc-

amine substructure contributed to stronger intramolecular CT tural change signicantly aﬀected its LUMO energy and HOMO

interaction.

structure to suppress the CT interaction between the anthra-

Tetrasubstituted derivatives have longer absorption among quinone p unit and sulfonamide substituents. We could

the derivatives with same substituents. For example, the prepare a color-tunable anthraquinone dye library (l_max: 331–

absorption

of

tetrasubstituted

derivative

19

with 758 nm, l_end: 400–855 nm) that extended into the NIR region.

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Fig. 7 HOMO (top) and LUMO (bottom) of 1,4-disubstituted anthraquinones 7–10 and 12.

1,5- and 1,8-disubstituted derivatives with weaker aniline donor

units.

Electrochemical properties and DFT calculations

To understand the huge diﬀerences in absorption among 1–23,

we performed cyclic voltammetry and DFT calculations. Fig. 6

and S2 (ESI†) summarize the results according to the substitu-

tion position and the substituent, respectively. The compounds

show reversible reduction peaks and irreversible (some revers-

ible) oxidation peaks at ꢀ0.52 to ꢀ1.00 V (E_pc1), ꢀ0.54 to

ꢀ1.51 V (E_pc2) and 0.60–1.61 V (E_pa1) vs. Ag/AgCl, respectively,

which is accounted for by reduction of the electron-accepting

anthraquinone core and oxidation of the electron-donating

terminal arylamino/arylsulfonamide group. In the reduction

process, compounds with arylsulfonamide substituents (3, 4, 9,

10, 14, 15, 20, 21) showed a signicant anodic shi (E_pc1: ꢀ0.21

to ꢀ0.61 V) compared to other compounds (ꢀ0.82 to ꢀ1.00 V),

which is accounted for by an eﬀective intramolecular N–H/O]

C hydrogen bonding eﬀect between electron-donating arylsul-

fonamide groups and the electron-accepting anthraquinone

core.⁵²On the other hand, the reduction potential of other

compounds was almost equal to that of anthraquinone, which

indicates that an intramolecular N–H/O]C hydrogen

bonding eﬀect did not work eﬀectively for arylaminoan-

thraquinones without an electron-accepting sulfone unit. In the

oxidation process, its potentials were mainly governed by the

electron-donating unit. For example, compounds with stronger

electron-donating dialkylaminophenylamino units showed

a signicant cathodic shi of the oxidation peak. 1,4-Disubsti-

tuted and 1,8-tetrasubstituted derivatives with stronger p-phe-

nylenediamine donor units are stronger electron donors than

The theoretically calculated HOMO–LUMO energy and

simulated absorption by DFT calculations well reproduced the

trend in the experimental results. Fig. 7 and S3–S6 (ESI†) show

the HOMO and LUMO of 1,4-disubstituted derivatives 7–10, 12

and other compounds 1–6, 11, 13–23 for their optimized

structures. N–H units faced a carbonyl unit to form intra-

molecular hydrogen bonding interaction in all non-N-methyl-

ated derivatives. HOMO was located on an electron-donating p-

phenylenediamine/aniline substructure whereas LUMO was

located on an electron-accepting central p-quinone substruc-

ture. Since HOMO/LUMO were both co-located on the same p-

conjugated plane, transition-allowed intramolecular CT

occurred eﬀectively to induce a signicant bathochromic shi

depending on the electron-donating unit. Since similar intra-

molecular hydrogen bonding interaction was observed in all

N–H compounds, intramolecular N–H/O]C hydrogen

bonding contributed to their frontier orbitals. LUMO was

located on N–H nitrogen atoms in all N–H compounds, in

addition to an anthraquinone unit, which decreased its energy

through intramolecular N–H/O]C hydrogen bonding, as

observed in their cyclic voltammetry measurement, which

resulted in a signicant bathochromic shi in the UV-Vis

spectra (hydrogen-bond-assisted CT interaction). The degree

of modulation of LUMO energy through intramolecular

hydrogen bonding interaction diﬀers between the compounds

depending on the substituents. The LUMO energies of sulfon-

amide derivatives were more reduced through N–H/O]C

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hydrogen bonding, as demonstrated by comparison with the NICOLET 6700 FT-IR spectrometer with a resolution of 4 cm^ꢀ1

.

corresponding N–Me derivatives without intramolecular UV-Vis spectra were measured in CH₂Cl₂(for spectrochemical

hydrogen bonding interaction. On the other hand, the LUMO analysis). Cyclic voltammetry was performed in dry CH₂Cl₂

energies of other derivatives with arylamino groups was less containing 0.1 M Bu₄NBF₄with a scan rate of 100 mV s^ꢀ1. A

inuenced through intramolecular N–H/O]C hydrogen glassy carbon electrode, Pt electrode and Ag/AgCl electrode were

bonding, which could be accounted for by the diﬀerent orbital used as the working, counter, and reference electrodes,

contributions of frontier orbitals between compounds with/ respectively.

without an electron-accepting sulfone unit. N-Methylation of

sulfonamide derivatives also aﬀected the LUMO energy and

absorption spectra, since it induced a drastic structural change

from a coplanar arrangement to an orthogonal relationship

between the anthraquinone scaﬀold and arylsulfonamide

substituents, which suppresses intramolecular N–H/O]C

hydrogen bonding and forbits eﬀective HOMO–LUMO

transition.

Single-crystal X-ray structure analysis

Crystallographic data were collected using a diﬀractometer

equipped with a rotating anode tted with a multilayer confocal

ꢀ

optic using Cu-K_a(l ¼ 1.54187 A) radiation. Structure rene-

ments were carried out using the full-matrix least-squares

method on F². Calculations were performed using the Crystal

Structure and SHELEX soware packages.⁶⁶Parameters were

rened using anisotropic temperature factors except for the

hydrogen atom.

Conclusion

We prepared a series of arylaminoanthraquinone derivatives

including those with electron-accepting sulfone units and

electron-donating dialkylamino units. As demonstrated in UV-

Vis spectra, we could prepare a color-tunable anthraquinone

library that reached into the NIR region through the precise

control of frontier orbitals. Fine color-tuning was achieved

through proper selection and positioning of the substituents.

Eﬀective intramolecular hydrogen-bond-assisted CT interaction

between electron-donating aniline/p-phenylenediamine and

electron-accepting anthraquinone substructures induced

a signicant bathochromic shi for the anthraquinone. The

introduction of an electron-accepting sulfone unit between

amino and aryl units signicantly modulated the photophysical

properties. Substitution of a terminal alkyl group with an

electron-donating dialkylamino unit also aﬀected the optical

properties, which is suitable for ne color-tuning. The number

and position of the substituent also signicantly contributed to

determine the photophysical properties. Especially, tetrasub-

stituted derivatives showed a larger red shi compared to other

derivatives due to the orbital degeneracy of stronger electron-

donating p-phenylenediamine substructures. The change in

conformation induced by N-methylation at the congested peri-

position of the anthraquinone unit suppressed the interaction

between the anthraquinone p unit and sulfonamide substitu-

ents to induce a signicant hypochromic shi.

Crystal data of 22

Single crystal of 22 suitable for single-crystal structure analysis

was obtained by recrystallization from MeCN. Black plate.

ꢀ

C

₄₂H₄₈N₆O₆S₂, M ¼ 797.00, P1 bar (#2), a ¼ 10.2153(8) A, b ¼

ꢁ

ꢀ

14.5679(11) A, c ¼ 16.0551(12) A, a ¼ 107.972(8) , b ¼

ꢀ³

ꢁ

104.609(7) , g ¼ 106.675(8) , V ¼ 2019.1(3) A , Z ¼ 2, D_c

¼

1.311 g cm^ꢀ3. Independent reection 7246 (all), T ¼ 173 K, m ¼

16.46 cm^ꢀ1, R ¼ 6.57%. CCDC 2063387.†

Computational methods

67

DFT calculations were performed with the Gaussian 09

or

Gaussian 16 ⁶⁸program packages. The geometries of the mole-

cules were optimized using the B3LYP/6-31G* basis set.

Terminal long alkyl groups were replaced by methyl groups in

13, 15, 19 and 21. Stationary points were assessed by a vibration

frequency analysis. TD-DFT calculations were performed for the

optimized structure with the B3LYP/cc-pvdz basis set.

Preparation of 1

A mixture of 1,8-dichloroanthraquinone (847 mg, 3.06 mmol),

toluidine (974 mg, 9.09 mmol) and CsCO₃(3.90 g, 20.2 mmol) in

dry toluene (45 mL) was degassed by bubbling with N₂.

Pd₂(dba)₃(109 mg, 119 mmol) and (ꢂ)-BINAP (327 mg, 525

ꢁ

mmol) were added at rt. The mixture was stirred at 110 C for

38 h. The reaction was cooled to rt, and the solvent was removed

under reduced pressure. The obtained product was dissolved in

CH₂Cl₂and H₂O. The aqueous layer was separated and extrac-

ted with CH₂Cl₂. The combined organic layer was dried over

MgSO₄. Aer evaporation of the solvent under reduced pres-

sure, the obtained crude product was puried by silica gel

column chromatography (toluene) to give 1 (1.26 g, 98%) as

a dark purple solid. The spectroscopic data were identical to the

reported values.⁵⁸

Experimental section

General methods

Commercially available reagents and solvents were used

without further purication. NMR spectra were measured in

CDCl₃on a Bruker Avance III 400 or a Bruker Avance III 500

NMR spectrometer. Chemical shis (d) in ppm were referenced

to an internal standard of tetramethylsilane (¹H) or residual

nondeuterated solvent (¹³C: 77.0 ppm for CDCl₃). Mass spectra

were obtained in EI or FAB mode with a JMS-700 mass spec-

trometer at the NMR and MS Laboratory, Graduate School of

Preparation of 2 and 5

Agriculture, Tohoku University. Infrared (IR, 400–4000 cm^ꢀ1

)

A mixture of 1,8-dichloroanthraquinone (850 mg, 3.07 mmol),

spectra were measured on a KBr pellet with a Thermo Scientic N,N-dimethyl-1,4-phenylenediamine (1.15 mL, 9.20 mmol) and

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CsCO₃(4.14 g, 21.5 mmol) in dry toluene (40 mL) was degassed

C

₂₈H₂₂N₂O₆S₂: C, 61.52 H, 4.06; N, 5.12. Found: C, 61.49 H,

by bubbling with N₂. Pd₂(dba)₃(140 mg, 153 mmol) and 4.21; N, 5.07.

(ꢂ)-BINAP (382 mg, 613 mmol) were added at rt. The mixture was

stirred at 110 ^ꢁC for 36 h. The reaction was cooled to rt, and the Preparation of 4

mixture was diluted with CHCl₃and H₂O. The aqueous layer

A mixture of 1,8-dichloroanthraquinone (1.11 g, 4.00 mmol), 4-

was separated and extracted with CHCl₃. The combined organic

layer was washed with brine and dried over MgSO₄. Aer

evaporation of the solvent under reduced pressure, the obtained

crude product was puried by silica gel column chromatog-

raphy (CHCl₃), followed by GPC to give 2 (908 mg, 62%) and 5

(242 mg, 21%) as a dark blue solid and a dark purple solid,

respectively.

(dimethylamino)benzenesulfonamide (2.00 g, 9.99 mmol),⁶⁵

copper(II) acetate monohydrate (96.1 mg, 481 mmol) and

potassium acetate (995 mg, 10.1 mmol) in nitrobenzene (40 mL)

ꢁ

was stirred at 200 C under air for 16 h. Aer cooling to rt, the

resulting mixture was diluted with water and CHCl₃. The

aqueous layer was separated and extracted with CHCl₃. The

combined organic layers were washed with brine and dried over

MgSO₄. Aer evaporation of the solvent under reduced pres-

sure, the obtained crude product was suspended in toluene/

EtOH (1/1, ꢃ100 mL) and the insoluble material was collected

by ltration. The obtained solid was repeatedly recrystallized

from toluene/EtOH to give compound 4 (1.03 g, 43%) as a dark

orange solid.

Data for 2. Mp 276–277 ^ꢁC; ¹H NMR (400 MHz): d 11.1 (s, 2H),

7.61 (dd, J ¼ 7.3, 1.2 Hz, 2H), 7.36 (dd, J ¼ 8.5, 7.3 Hz, 2H), 7.26

(dd, J ¼ 8.5, 1.2 Hz, 2H), 7.17 (d, J ¼ 8.8 Hz, 4H), 6.77 (d, J ¼

8.8 Hz, 4H), 2.97 (s, 12H). ¹³C NMR (100 MHz): d 188.7, 184.3,

150.6, 148.6, 134.3, 133.7, 128.7, 126.7, 120.0, 116.3, 114.6,

113.3, 40.8. IR: 1656, 1612, 1561, 1522, 1494, 1477, 1440, 1392,

1373, 1350, 1294, 1236, 1216, 1182, 1166, 1126, 1089, 1066, 945,

866, 839, 817, 804, 750, 606 cm^ꢀ1. HRMS (EI) calcd for

Mp: 278–280 ^ꢁC. ¹H NMR (400 MHz): d 11.72 (s, 2H), 8.03 (dd,

J ¼ 8.5, 1.2 Hz, 2H), 7.88 (dd, J ¼ 7.6, 1.2 Hz, 2H), 7.78 (d, J ¼

9.2 Hz, 4H), 7.63 (t, J ¼ 8.0 Hz, 2H), 6.62 (d, J ¼ 9.2 Hz, 4H), 3.01

(s, 12H). ¹³C NMR (100 MHz): d 190.4, 181.9, 153.2, 141.9, 135.6,

133.6, 129.2, 123.9, 123.8, 121.8, 117.9, 110.9, 40.0. IR: 3112,

2904, 2822, 1672, 1618, 1599, 1552, 1522, 1476, 1455, 1380,

1344, 1298, 1264, 1222, 1148, 1089, 989, 944, 873, 852, 815, 70,

749, 715, 701, 674, 661, 643, 557, 544, 516, 460 cm^ꢀ1. HRMS

(FAB) calcd for C₃₀H₂₈N₄O₆S₂Na: 627.1348 [(M + Na)⁺]; found:

627.1350. Anal. calcd for C₃₀H₂₈N₄O₆S₂$0.5(toluene): C, 61.83

H, 4.96; N, 8.61. Found: C, 61.90 H, 4.95; N8.60.

C

₃₀H₂₈O₂N₄476.2212 (M⁺); found: 476.2213. Anal. calcd for

₃₀H₂₈O₂N₄$0.33 H₂O: C, 74.67; H, 5.99; N, 11.61; found: C,

74.69; H, 5.86; N 11.44.

Data for 5. Mp 203–204 ^ꢁC; ¹H NMR (CDCl₃): d 11.03 (s, 1H),

8.28 (dd, J ¼ 7.7, 1.4 Hz, 1H), 7.79 (dd, J ¼ 8.0, 1.4 Hz, 1H), 7.61

(t, J ¼ 7.8 Hz, 1H), 7.59 (dd, J ¼ 7.3, 1.2 Hz, 1H), 7.40–7.38 (m,

1H), 7.30 (dd, J ¼ 8.7, 1.2 Hz, 1H), 7.16 (d, J ¼ 8.8 Hz, 2H), 6.77

(d, J ¼ 8.8 Hz, 2H), 2.99 (s, 6H).¹³C NMR (CDCl₃): d 184.1, 182.9,

151.0, 148.8, 138.0, 135.6, 134.54, 134,51, 133.5, 132.7, 130.8,

128.0, 126.7, 126.5, 120.7, 116.4, 114.1, 113.2, 40.7. IR: 1665,

1630, 1615, 1594, 1577, 1526, 1357, 1310, 1243, 1184, 1131,

1064, 838, 788, 741 cm^ꢀ1. HRMS (EI) calcd for C₂₂H₁₇O₂N₂Cl

376.0979 (M⁺); found: 376.0977. Anal. calcd for C₂₂H₁₇O₂N₂Cl:

C, 70.12; H, 4.55; N, 7.43; found: C, 70.20; H, 4.55; N 7.16.

55

Preparation of 6

To a suspension of NaH (60% in oil, 333 mg, 8.33 mmol) in dry

DMF (20 mL) was added 3 (303 mg, 554 mmol) under N₂. The

mixture was stirred at rt for 45 min. To the resulting solution

was added MeI (700 mL, 11.0 mmol) at this temperature. The

mixture was stirred at rt for 12 h. The mixture was diluted with

an excess amount of water. The resulting precipitate was

collected by ltration, washed with water, and then dried under

vacuum. Recrystallization from EtOH gave 6 (171 mg, 54%) as

an orange crystalline solid.

52

Preparation of 3

A mixture of 1,8-dichloroanthraquinone (5.01 g, 18.1 mmol), p-

toluenesulfonamide (9.20 g, 53.7 mmol), copper(^II) acetate

monohydrate (250 mg, 1.25 mmol) and potassium acetate

(4.00 g, 40.8 mmol) in nitrobenzene (50 mL) was stirred at

200 ^ꢁC under air for 14.5 h. Aer cooling to rt, the resulting

mixture was diluted with water and CHCl₃. The aqueous layer

was separated and extracted with CHCl₃. The combined organic

layers were washed with brine and dried over MgSO₄. Aer

evaporation of the solvent under reduced pressure, the obtained

crude product was recrystallized from benzene to give

compound 3 (6.16 g, 62%) as a yellow solid.

Mp: 236–237 ^ꢁC. ¹H NMR (400 MHz): d 8.24 (dd, J ¼ 7.8,

1.3 Hz, 2H), 7.70 (d, J ¼ 7.8 Hz, 4H), 7.63 (t, J ¼ 7.6 Hz, 2H), 7.47

(dd, J ¼ 7.8, 1.3 Hz, 2H), 7.31 (d, J ¼ 7.8 Hz, 4H), 3.24 (s, 6H),

2.43 (s, 6H). ¹³C NMR (100 MHz): d 182.6, 182.3, 143.5, 140.3,

136.0, 134.6, 133.6, 133.0, 129.6, 127.9, 126.9, 38.8, 21.6. IR:

3072, 2948, 2919, 1680, 1585, 1495, 1461, 1436, 1400, 1345,

1318, 1249, 1216, 1188, 1150, 1089, 1020, 1011, 957, 871, 850,

802, 752, 730, 688, 675, 651, 581, 563, 545, 517 cm^ꢀ1. HRMS

(FAB) calcd for C₃₀H₂₇N₂O₆S₂: 575.1311 [(M + H)⁺]; found:

575.1309. Anal. calcd for C₃₀H₂₆N₂O₆S₂: C, 62.70 H, 4.56; N,

4.87. Found: C, 62.55 H, 4.73; N, 4.78.

Mp: 274–275 ^ꢁC. ¹H NMR (400 MHz): d 11.8 (s, 2H), 8.02 (dd, J

¼ 8.5, 1.2 Hz, 2H), 7.92 (dd, J ¼ 7.5, 1.2 Hz, 2H), 7.86 (d, J ¼

8.5 Hz, 4H), 7.65 (br t, J ¼ 8.1 Hz, 2H), 7.30 (d, J ¼ 8.1 Hz, 4H),

2.38 (s, 6H). ¹³C NMR (100 MHz): d 190.6, 181.5, 144.6, 141.5,

136.2, 135.9, 133.6, 130.0, 127.3, 123.9, 122.3, 118.0, 21.6 IR:

3129, 1668, 1619, 1596, 1575, 1483, 1459, 1386, 1343, 1299,

Preparation of 8 and 11

1263, 1236, 1160, 1090, 993, 886, 863, 844, 812, 743, 718, 664, A mixture of 1,4-dichloroanthraquinone (854 mg, 3.08 mmol),

563, 544, 513, 464 cm^ꢀ1. HRMS (FAB) calcd for C₂₈H₂₃N₂O₆S₂: N,N-dimethyl-1,4-phenylenediamine (1.25 mL, 10.0 mmol) and

547.0998 [(M

+

H)⁺]; found: 547.0992. Anal. calcd for CsCO₃(4.34 g, 22.5 mmol) in dry toluene (40 mL) was degassed

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by bubbling with N₂. Pd₂(dba)₃(140 mg, 153 mmol) and Anal. calcd for C₂₈H₂₂N₂O₆S₂: C, 61.52 H, 4.06; N, 5.12. Found:

(ꢂ)-BINAP (402 mg, 646 mmol) were added at rt. The mixture was C, 61.60 H, 4.31; N,5.05.

stirred at 110 ^ꢁC for 47 h. The reaction was cooled to rt, and the

mixture was diluted with CHCl₃and H₂O. The aqueous layer

was separated and extracted with CHCl₃. The combined organic

layer was washed with brine and dried over MgSO₄. Aer

evaporation of the solvent under reduced pressure, the obtained

crude product was puried by silica gel column chromatog-

raphy (CHCl₃), followed by recrystallization (EtOH for 8, EtOH/

CHCl₃for 11) to give 8 (234 mg, 16%) and 11 (742 mg, 64%) as

a dark green solid and a dark purple solid, respectively.

Preparation of 10

Route A. A mixture of 1,4-diaminoanthraquinone (776 mg,

3.26 mmol) and 4-(dimethylamino)benzenesulfonyl chloride

(1.50 g, 6.84 mmol)⁶⁵in dry pyridine (40 mL) was stirred at rt for

ꢁ

24 h and then at 70 C for 15 h. Aer cooling to rt, the solvent

was removed under reduced pressure. The resulting mixture

was dissolved in CHCl₃and the solution was washed with brine

and dried over MgSO₄. Aer evaporation of the solvent under

reduced pressure, the obtained crude product was recrystallized

from toluene/EtOH to give 10 (803 mg, 41%) as a red solid.

Mp: 287–288 ^ꢁC. ¹H NMR (400 MHz): d 12.25 (s, 2H), 8.24 (dd,

J ¼ 5.9, 3.3 Hz, 2H), 7.95 (s, 2H), 7.79 (dd, J ¼ 5.9, 3.3 Hz, 2H),

1

ꢁ

Data for 8. Mp 262–264 C; H NMR (400 MHz): d 12.34 (s,

2H), 8.41 (dd, J ¼ 5.9, 3.4 Hz, 2H), 7.74 (dd, J ¼ 5.9, 3.4 Hz, 2H),

7.31 (s, 2H), 7.14 (d, J ¼ 8.8 Hz, 4H), 6.75 (d, J ¼ 8.8 Hz, 4H), 2.97

(s, 12H).¹³C NMR (100 MHz): d 182.3, 148.5, 145.5, 134.5, 132.2,

128.3, 126.3, 126.1, 125.2, 113.2, 110.0, 40.8. IR: 1611, 1589,

1567, 1547, 1521, 1501, 1458, 1440, 1401, 1364, 1339, 1258,

1216, 1187, 1162, 1132, 1069, 1027, 1007, 967, 944, 922, 881,

7.69 (d, J ¼ 9.1 Hz, 4H), 6.58 (d, J ¼ 9.1 Hz, 4H), 2.99 (s, 12H). ¹³

C

NMR (125 MHz): d 186.2, 153.1, 137.7, 134.5, 133.1, 129.2, 127.2,

126.2, 123.9, 116.6, 110.9, 40.0. IR: 3448, 3098, 2896, 1639, 1597,

1552, 1521, 1473, 1449, 1375, 1349, 1326, 1286, 1253, 1206,

1153, 1091, 1069, 998, 970, 919, 892, 836, 824, 816, 794, 773, 728,

708, 642, 558, 544 cm^ꢀ1. HRMS (FAB) calcd for C₃₀H₂₈N₄O₆S₂-

Na: 627.1348 [(M + Na)⁺]; found: 627.1347. Anal. calcd for

850, 823, 800, 755, 727, 673, 640, 607, 562, 517, 466, 432 cm^ꢀ1

HRMS (EI) calcd for

₃₀H₂₈O₂N₄476.2212 (M⁺); found:

.

C

476.2211. Anal. Calcd for C₃₀H₂₈O₂N₄$2H₂O: C, 70.29; H,

6.29; N, 10.93; found: C, 70.32; H, 6.12; N 10.93.

Data for 11. Mp 195–197 ^ꢁC; ¹H NMR (400 MHz): d 11.51 (s,

1H), 8.29–8.23 (m, 2H), 7.80–7.71 (m, 2H), 7.37 (dd, J ¼ 9.5,

0.5 Hz, 1H), 7.19 (d, J ¼ 9.5 Hz, 1H), 7.14 (d, J ¼ 8.8 Hz, 2H), 6.77

(d, J ¼ 8.8 Hz, 1H), 2.99 (s, 6H).¹³C NMR (125 MHz): d 184.4,

183.0, 150.6, 149.0, 138.7, 133.9, 133.8, 133.7, 133.3, 129.9,

127.4, 126.9, 126.8, 126.3, 123.0, 120.8, 114.1, 113.2, 40.7. IR:

1668, 1625, 1610, 1586, 1576, 1521, 1491, 1480, 1444, 1355,

1293, 1257, 1240, 1181, 1125, 807, 734, 722 cm^ꢀ1. HRMS (EI)

calcd for C₂₂H₁₇O₂N₂Cl 376.0979 (M⁺); found: 376.0977. Anal.

Calcd for C₂₂H₁₇O₂N₂Cl: C, 70.12; H, 4.55; N, 7.43; found: C,

70.16; H, 4.51; N 7.30.

C

₃₀H₂₈N₄O₆S₂$0.33 toluene: C, 61.12 H, 4.86; N, 8.82. Found: C,

61.22 H, 5.06; N, 8.86.

Route B. A mixture of 1,4-dichloroanthraquinone (570 mg,

2.06 mmol), 4-(dimethylamino)benzenesulfonamide (1.00 g,

4.50 mmol), copper(^II) acetate monohydrate (73.3 mg, 367 mmol)

and potassium acetate (540 mg, 5.50 mmol) in nitrobenzene (40

mL) was stirred at 200 ^ꢁC under air for 15 h. Aer cooling to rt,

the resulting mixture was diluted with water and CHCl₃. The

aqueous layer was separated and extracted with CHCl₃. The

combined organic layers were washed with brine and dried over

MgSO₄. Aer evaporation of the solvent under reduced pres-

sure, the obtained crude product was recrystallized from

toluene/EtOH to give compound 10 (292 mg, 23%) as a red solid.

The spectroscopic data were identical to those for the product

synthesized through route A.

52

Preparation of 9

A mixture of 1,4-dichloroanthraquinone (5.00 g, 18.1 mmol), p-

toluenesulfonamide (9.20 g, 53.7 mmol), copper(^II) acetate

monohydrate (250 mg, 1.25 mmol), and potassium acetate

(4.00 g, 40.8 mmol) in nitrobenzene (50 mL) was stirred at

55

Preparation of 12

200 ^ꢁC under air for 10 h. Aer cooling to rt, the resulting A mixture of 9 (200 mg, 366 mmol), K₂CO₃(506 mg, 3.66 mmol)

mixture was diluted with water and CHCl₃. The aqueous layer and MeI (455 mL, 7.32 mmol) in DMF (10 mL) was stirred at

was separated and extracted with CHCl₃. The combined organic 50 ^ꢁC for 13.5 h in a sealed glass pressure vessel. Aer cooling to

layers were washed with brine and dried over MgSO₄. The ob- rt, the mixture was diluted with H₂O. The resulting precipitate

tained crude solid was washed with a small amount of CHCl₃was collected by ltration, washed with H₂O, and then dried

and then recrystallized from CHCl₃to give compound 9 (2.04 g) under vacuum. Recrystallization from CHCl₃/EtOH gave 12

as a red solid. Combined ltrate was subjected to silica gel (195 mg, 93%) as a yellow solid.

column chromatography (CHCl₃) to give an additional amount

Mp: 228–229 ^ꢁC (decomp.). ¹H NMR (400 MHz, 50 ^ꢁC): d 7.92

(br s, 2H), 7.68 (dd, J ¼ 5.7, 3.2 Hz, 2H), 7.57 (t, J ¼ 8.2 Hz, 4H),

of compound 9 (5.18 g). Total yield: 7.22 g (73%).

Mp: 245–246 ^ꢁC. ¹H NMR (400 MHz): d 12.3 (s, 2H), 8.22 (dd, J 7.42 (s, 2H), 7.23 (d, J ¼ 8.2 Hz, 4H), 3.35 (s, 6H), 2.39 (s, 6H). ¹³

C

¼ 9.2, 5.9 Hz, 2H), 7.97 (s, 2H), 7.80 (dd, J ¼ 9.2, 5.9 Hz, 2H), 7.76 NMR (125 MHz, 50 ^ꢁC): d 182.5, 143.5, 140.3, 136.5, 136.4, 134.2,

(d, J ¼ 8.2 Hz, 4H), 7.24 (d, J ¼ 8.2 Hz, 4H), 2.36 (s, 6H). ¹³C NMR 134.1, 133.6, 129.6, 127.7, 126.6, 38.8, 21.5. IR: 1670, 1590, 1463,

(100 MHz): d 186.2, 144.5, 137.4, 136.3, 134.8, 132.9, 129.9, 1348, 1322, 1305, 1254, 1201, 1156, 1087, 931, 910, 877, 809,

127.3, 127.2, 126.3, 117.1, 21.5. IR: 3019, 1639, 1590, 1475, 1379, 795, 727, 713, 679, 636, 596, 549, 516 cm^ꢀ1. HRMS (FAB) calcd

1352, 1287, 1254, 1186, 1164, 1090, 1072, 971, 920, 896, 859, for C₃₀H₂₇N₂O₆S₂: 575.1311 [(M + H)⁺]; found: 575.1310. Anal.

839, 818, 726, 714, 656, 579, 558, 544 cm^ꢀ1. HRMS (FAB) calcd calcd for C₃₀H₂₆N₂O₆S₂: C, 62.70 H, 4.56; N, 4.87. Found: C,

for C₂₈H₂₂N₂O₆S₂Na: 569.0817 [(M + Na)⁺]; found: 569.0817. 62.88 H, 4.57; N, 4.82.

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d 152.6, 129.6, 128.4, 110.3, 50.9, 29.0, 20.2, 13.9. IR: 2959, 2933,

Preparation of 13

2873, 1591, 1516, 1467, 1409, 1368, 1314, 1292, 1165, 1086, 992,

A mixture of 1,5-dichloroanthraquinone (845 mg, 3.05 mmol), 4-

tert-butylaniline (1.45 mL, 9.13 mmol) and CsCO₃(3.91 g, 20.3

mmol) in dry toluene (40 mL) was degassed by bubbling with

N₂. Pd₂(dba)₃(117 mg, 127 mmol) and (ꢂ)-BINAP (333 mg, 535

926, 814, 655, 559, 542, 501 cm^ꢀ1. HRMS (EI) calcd for C₁₄

H₂₂ClNO₂S: 303.1060 [(M + H)⁺]; found: 303.1062.

-

ꢁ

mmol) were added at rt. The mixture was stirred at 110 C for

Preparation of 15

38 h. The reaction was cooled to rt, and the resulting solid was

collected by ltration and washed with toluene to give 13

(1.29 g, 84%) as a dark purple crystalline solid. The spectro-

scopic data were identical to the reported values.⁵⁸

A mixture of 1,5-diaminoanthraquinone (991 mg, 4.16 mmol)

and 4-(dibutylamino)benzenesulfonyl chloride (2.65 g, 8.74

mmol) in dry pyridine (50 mL) was stirred at 70 ^ꢁC for 45 h. Aer

cooling to rt, the solvent was removed under reduced pressure.

The resulting mixture was dissolved in CHCl₃and the solution

was washed with brine and dried over MgSO₄. Aer evaporation

of the solvent under reduced pressure, the obtained crude

product was recrystallized from toluene/EtOH to give 15 (2.12 g,

66%) as a red-brown solid.

52

Preparation of 14

A mixture of 1,5-dichloroanthraquinone (4.71 g, 17.0 mmol), 4-

tert-butylbenzenesulfonamide (10.0 g, 46.9 mmol), copper(^II)

acetate monohydrate (218 mg, 1.09 mmol), and potassium

acetate_ꢁ(3.49 g, 35.6 mmol) in nitrobenzene (50 mL) was stirred

at 200 C under air for 11.5 h. Aer cooling to rt, the resulting

mixture was diluted with water and CHCl₃. The aqueous layer

was separated and extracted with CHCl₃. The combined organic

layers were washed with brine and dried over MgSO₄. Aer

evaporation of the solvent under reduced pressure, the obtained

solid was subjected to silica gel column chromatography

(CHCl₃) followed by recrystallization from toluene to give

compound 14 as a yellow solid (6.82 g, 63%).

Mp: 256–257 ^ꢁC. ¹H NMR (400 MHz): d 11.97 (s, 2H), 8.01 (dd,

J ¼ 8.5, 1.1 Hz, 2H), 7.93 (dd, J ¼ 7.7, 1.1 Hz, 2H), 7.69 (d, J ¼

9.2 Hz, 4H), 7.66 (sext, J ¼ 8.0 Hz, 2H), 6.52 (d, J ¼ 9.2 Hz, 4H),

3.24 (t, J ¼ 7.8 Hz, 8H), 1.55–1.46 (m, 8H), 1.31 (sext, J ¼ 7.6 Hz,

8H), 0.92 (t, J ¼ 7.3 Hz, 12H). ¹³C NMR (100 MHz): d 185.8, 151.4,

141.8, 135.6, 134.6, 129.3, 123.1, 121.8, 116.6, 110.4, 50.7, 29.0,

20.2, 13.9. IR: 3455, 3094, 2957, 2930, 2871, 1637, 1593, 1509,

1474, 1379, 1348, 1261, 1228, 1207, 1151, 1092, 1054, 995, 929,

917, 881, 825, 813, 774, 734, 715, 707, 654, 608, 566, 550, 514,

443, 418 cm^ꢀ1. HRMS (FAB) calcd for C₄₂H₅₂N₄O₆S₂Na:

795.3226 [(M + Na)⁺]; found: 795.3228. Anal. calcd for C₄₂H₅₂-

N₄O₆S₂$toluene: C, 65.26 H, 6.78; N, 7.25. Found: C, 65.42 H,

6.82; N, 7.16.

Mp: >300 ^ꢁC. ¹H NMR (400 MHz): d 12.1 (s, 2H), 7.99 (dd, J ¼

8.5, 1.1 Hz, 2H), 7.96 (dd, J ¼ 7.7, 1.1 Hz, 2H), 7.87–7.83 (m, 4H),

7.68 (t, J ¼ 8.2 Hz), 7.49–7.44 (m, 4H), 1.26 (s, 18H). ¹³C NMR

(100 MHz): d 185.8, 157.4, 141.3, 136.2, 135.8, 134.5, 127.1,

126.3, 123.4, 122.5, 116.9, 35.2, 30.9. IR: 3080, 2965, 1637, 1593,

1475, 1385, 1348, 1264, 1199, 1163, 1113, 1086, 1055, 889, 835,

770, 753, 711, 654, 624, 570, 548 cm^ꢀ1. HRMS (FAB) calcd for

Preparation of 16

C

₃₄H₃₅N₂O₆S₂: 631.1937 [(M + H)⁺]; found: 631.1937. Anal. calcd

A mixture of 1,5-dichloroanthraquinone (850 mg, 3.07 mmol),

N,N-dimethyl-1,4-phenylenediamine (1.25 mL, 10.0 mmol) and

CsCO₃(4.14 g, 21.5 mmol) in dry toluene (40 mL) was degassed

by bubbling with N₂. Pd₂(dba)₃(176 mg, 192 mmol) and

(ꢂ)-BINAP (470 mg, 755 mmol) were added at rt. The mixture was

for C₃₄H₃₄N₂O₆S₂: C, 64.74 H, 5.43; N, 4.44. Found: C, 64.90 H,

5.49; N, 4.37.

Preparation of 4-(dibutylamino)benzenesulfonyl chloride

A mixture of N,N-dibutylaniline (8.47 g, 41.2 mmol) and bis(- stirred at 110 ^ꢁC for 42 h. The reaction was cooled to rt, and the

ꢁ

trimethylsilyl) sulfate (10.0 g, 41.2 mmol) was stirred at 170 C resulting mixture was diluted with water and CHCl₃. The

under a nitrogen atmosphere for 4 h. Aer cooling to rt, the aqueous layer was separated and extracted with CHCl₃. The

resulting solid was washed with ether and H₂O, and then dried combined organic layers were washed with brine and dried over

under vacuum to give 4-(dibutylamino)benzenesulfonic acid, MgSO₄. Aer evaporation of the solvent under reduced pres-

which was used for the next reaction directly without further sure, the resulting purple solid was subjected to silica gel

purication. To the obtained 4-(dibutylamino)benzenesulfonic column chromatography (CHCl₃) to give 16 (694 mg, 61%) as

acid in dry CH₂Cl₂(110 mL) was added PCl₅(8.59 g, 41.2 mmol) a dark purple crystalline solid.

at 0 ^ꢁC. The mixture was warmed gradually to rt and stirred for

Mp: 213–214 ^ꢁC. ¹H NMR (400 MHz): d 11.04 (s, 1H), 8.34 (dd,

24 h under a nitrogen atmosphere. The solvent was removed J ¼ 7.7, 1.4 Hz, 1H), 7.74 (dd, J ¼ 8.0, 1.4 Hz, 1H), 7.66 (t, J ¼

under reduced pressure and the product was dissolved in ether. 7.9 Hz, 1H), 7.60 (dd, J ¼ 7.3, 1.1 Hz, 1H), 7.44 (dd, J ¼ 8.5,

The solution was washed with H₂O and dried over MgSO₄. Aer 7.5 Hz, 1H), 7.17 (d, J ¼ 8.8 Hz, 2H), 6.78 (d, J ¼ 8.8 Hz, 2H), 2.99

evaporation of the solvent under reduced pressure, the crude (s, 6H). ¹³C NMR (100 MHz): d 183.3, 182.5, 150.8, 148.9, 137.6,

product was subjected to silica gel column chromatography 136.5, 135.6, 135.2, 134.5, 133.4, 129.4, 127.8, 126.7, 126.3,

(hexane/ether ¼ 100/20) to give 4-(dibutylamino)benzene- 119.4, 117.2, 113.2, 112.5, 40.7. IR: 1665, 1627, 1591, 1577, 1566,

sulfonyl chloride (8.19 g, 65% in two steps) as a yellow oil.

1522, 1500, 1308, 1258, 1224, 1193, 1158, 808, 760, 709 cm^ꢀ1

.

¹H NMR (400 MHz): d 7.79 (d, J ¼ 9.4 Hz, 2H), 6.62 (d, J ¼ HRMS (EI) calcd for C₂₂H₁₇N₂O₂Cl: 376.0979 (M⁺); found:

9.4 Hz, 2H), 3.36 (t, J ¼ 7.8 Hz, 4H), 1.65–1.55 (m, 4H), 1.38 (sext, 376.0976. Anal. calcd for C₂₂H₁₇N₂O₂Cl: C, 70.12 H, 4.55; N,

J ¼ 7.5 Hz, 4H) 0.98 (t, J ¼ 7.3 Hz, 6H). ¹³C NMR (100 MHz): 7.43. Found: C, 70.02 H, 4.58; N, 7.34.

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(7.80 g, 40.8 mmol) in dry toluene (50 mL) was degassed by

bubbling with N₂. Pd₂(dba)₃(110 mg, 120 mmol) and (ꢂ)-BINAP

(330 mg, 530 mmol) were added at rt. The mixture was stirred at

110 ^ꢁC for 49 h. The reaction was cooled to rt, and the resulting

crystalline solid was collected by ltration, washed with toluene

and H₂O, and dried under vacuum to give 19 (2.06 g, 86%) as

a dark green crystalline solid. The spectroscopic data were

identical to the reported values.⁵⁹

Preparation of 17

A mixture of 1,5-dichloroanthraquinone (1.17 g, 4.22 mmol), 4-

(dimethylamino)benzenesulfonamide (2.00 g, 10.0 mmol),

copper(^II) acetate monohydrate (125 mg, 626 mmol), and

potassium acetate (900 mg, 9.15 mmol) in nitrobenzene (80 mL)

was stirred at 200 ^ꢁC under air for 21.5 h. Aer cooling to rt, the

resulting mixture was diluted with water and CHCl₃. The

aqueous layer was separated and extracted with CHCl₃. The

combined organic layers were washed with brine and dried over

MgSO₄. Aer evaporation of the solvent under reduced pres-

sure, the obtained brown solid was recrystallized from toluene/

EtOH to remove insoluble material. Aer evaporation of the

solvent of the ltrate under reduced pressure, the obtained

solid was suspended in CHCl₃and ltered. The ltrate was

subjected to silica gel column chromatography (CHCl₃) to give

compound 17 as an orange solid (399 mg, 21%).

52

Preparation of 20

A mixture of 1,4,5,8-tetrachloroanthraquinone (3.00 g, 8.67

mmol), 4-tert-butylbenzenesulfonamide (10.0 g, 46.9 mmol),

copper(^II) acetate monohydrate (277 mg, 1.39 mmol), and

potassium acetate (3.57 g, 36.4 mmol) in nitrobenzene (50 mL)

was stirred at 200 ^ꢁC under air for 18.5 h. Aer cooling to rt, the

resulting mixture was diluted with water and CHCl₃. The

aqueous layer was separated and extracted with CHCl₃. The

combined organic layers were washed with brine and dried over

MgSO₄. The obtained crude solid was subjected to silica gel

column chromatography (CHCl₃) followed by recrystallization

from toluene to give compound 20 as a dark purple solid (5.11 g,

56%).

Mp: 245–247 ^ꢁC. ¹H NMR (400 MHz): d 11.85 (s, 1H), 8.30 (dd,

J ¼ 7.8, 1.4 Hz, 1H), 7.99 (dd, J ¼ 8.5, 1.1 Hz, 1H), 7.91 (dd, J ¼

7.7, 1.1 Hz, 1H), 7.79 (dd, J ¼ 8.0, 1.4 Hz, 1H), 7.76 (d, J ¼ 9.2 Hz,

2H), 7.69 (t, J ¼ 7.8 Hz, 1H), 7.66 (d, J ¼ 8.1 Hz, 1H), 6.59 (d, J ¼

9.2 Hz, 2H), 2.99 (s, 6H). ¹³C NMR (100 MHz): d 185.4, 181.2,

153.1, 141.4, 137.8, 136.3, 135.8, 135.3, 134.9, 133.8, 129.2,

129.1, 127.0, 123.9, 122.7, 122.1, 116.6, 110.8, 40.0. IR: 3097,

1675, 1636, 1598, 1573, 1553, 1523, 1477, 1468, 1447, 1380,

1340, 1322, 1285, 1268, 1208, 1197, 1149, 1093, 1071, 1036, 997,

935, 909, 846, 839, 812, 759, 708, 644, 557, 544, 431 cm^ꢀ1. HRMS

(FAB) calcd for C₂₂H₁₇N₂O₄SClNa: 463.0495 [(M + Na)⁺]; found:

463.0491. Anal. calcd for C₂₂H₁₇N₂O₄SCl: C, 59.93 H, 3.89; N,

6.35. Found: C, 59.79 H, 3.82; N, 6.23.

Mp: decomposed above 270 ^ꢁC. ¹H NMR (400 MHz): d 11.8 (s,

4H), 7.97 (s, 4H), 7.75 (d, J ¼ 8.7 Hz, 8H), 7.50 (d, J ¼ 8.7 Hz, 8H),

1.28 (s, 36H). ¹³C NMR (100 MHz): d 188.6, 157.8, 137.4, 136.0,

127.1, 126.6, 126.5, 116.9, 35.3, 30.9. IR: 2964, 1595, 1479, 1377,

1221, 1198, 1167, 1112, 1084, 981, 862, 837, 791, 755, 647, 622,

571, 546 cm^ꢀ1. HRMS (FAB) calcd for C₅₄H₆₀N₄O₁₀S₄Na:

1075.3090 [(M + Na)⁺]; found: 1075.3085. Anal. calcd for

C

₅₄H₆₀N₄O₁₀S₄: C, 61.57 H, 5.74; N, 5.32. Found: C, 61.81 H,

5.88; N, 5.24.

55

Preparation of 18

To a suspension of NaH (60% in oil, 380 mg, 9.51 mmol) in dry

DMF (30 mL) was added 14 (400 mg, 634 mmol) under N₂. The

mixture was stirred at rt for 45 min. To the resulting solution

was added MeI (790 mL, 12.7 mmol) at this temperature. The

mixture was stirred at rt for 16.5 h. The mixture was diluted with

an excess amount of water. The resulting precipitate was

collected by ltration, washed with water, and then dried under

vacuum. Recrystallization from CHCl₃/EtOH gave 18 (177 mg,

42%) as a yellow solid.

Preparation of 4-(dihexylamino)benzenesulfonyl chloride

A mixture of N,N-dihexylaniline (10.8 g, 41.3 mmol) and bi_ꢁs(-

trimethylsilyl) sulfate (10.0 g, 41.2 mmol) was stirred at 170 C

under a nitrogen atmosphere for 3 h. Aer cooling to rt, the

resulting solid was washed with ether and the dried under

vacuum to give 4-(dihexylamino)benzenesulfonic acid, which

was used for the next reaction directly without further puri-

cation. To the obtained 4-(dihexylamino)benzenesulfonic acid

in_ꢁdry CH₂Cl₂(110 mL) was added PCl₅(8.73 g, 41.9 mmol) at

0 C. The mixture was warmed gradually to rt and stirred for

41 h under a nitrogen atmosphere. The solvent was removed

under reduced pressure and the product was dissolved in ether.

The solution was washed with H₂O and dried over MgSO₄. Aer

evaporation of the solvent under reduced pressure, the crude

product was subjected to silica gel column chromatography

(hexane/ether ¼ 100/20) to give 4-(dihexylamino)benzene-

sulfonyl chloride (9.40 g, 63% in two steps) as a yellow oil.

¹H NMR (400 MHz): d 7.79 (d, J ¼ 9.3 Hz, 2H), 6.61 (d, J ¼

9.3 Hz, 2H), 3.34 (t, J ¼ 7.8 Hz, 4H), 1.67–1.57 (m, 4H), 1.38–1.29

(m, 4H), 0.91 (t, J ¼ 6.8 Hz, 6H). ¹³C NMR (125 MHz): d 152.6,

129.6, 128.6, 110.4, 51.2, 31.6, 26.9, 26.7, 22.6, 14.0. IR: 2957,

2931, 2859, 1591, 1516, 1469, 1409, 1369, 1164, 1087, 814, 656,

Mp: 268–270 ^ꢁC (decomp.). ¹H NMR (400 MHz, 50 ^ꢁC): d 8.08

(br d, J ¼ 7.8 Hz, 2H), 7.65(t, J ¼ 7.8 Hz, 2H), 7.63 (d, J ¼ 8.5 Hz,

4H), 7.50 (d, J ¼ 7.8 Hz, 2H), 7.44 (d, J ¼ 8.5 Hz, 4H), 3.35 (s, 6H),

13

ꢁ

1.33 (s, 18H). C NMR (125 MHz, 50 C): d 181.8, 156.4, 140.0,

137.0, 136.8, 136.4, 133.9, 127.9, 127.5, 125.8, 36.7, 35.2, 31.1.

IR: 3076, 2957, 1675, 1596, 1580, 1457, 1438, 1400, 1349, 1310,

1267, 1190, 1158, 1112, 1085, 1018, 877, 825, 807, 773, 756, 710,

626, 581, 552 cm^ꢀ1. HRMS (FAB) calcd for C₃₆H₃₉N₂O₆S₂:

659.2250 [(M

₃₆H₃₈N₂O₆S₂: C, 65.60 H, 5.81; N, 4.25. Found: C, 62.60 H,

5.86; N, 4.22.

+

H)⁺]; found: 659.2250. Anal. calcd for

C

Preparation of 19

A mixture of 1,4,5,8-tetrachloroanthraquinone (1.04 g, 3.01 561 cm^ꢀ1. HRMS (EI) calcd for C₁₈H₃₀NO₂SCl: 359.1686 (M⁺);

mmol), 4-tert-butylaniline (2.90 mL, 18.1 mmol) and CsCO₃found: 359.1685.

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was added MeI (710 mL, 11.4 mmol) at this temperature. The

mixture was stirred at rt for 17 h. The mixture was diluted with

an excess amount of water. The resulting precipitate was

collected by ltration, washed with water, and then dried under

vacuum. Recrystallization from CHCl₃/EtOH gave 23 (264 mg,

63%) as a yellow solid.

Preparation of 21

To a solution of 1,4,5,8-tetraaminoanthraquinone (Disperse

Blue 1, Aldrich, 1.45 g, 5.39 mmol) in dry pyridine (100 mL) was

added 4-(dihexylamino)benzenesulfonyl chloride (9.40 g, 24.2

mmol). The mixture was stirred at rt for 77 h under a nitrogen

atmosphere. Aer removal of the solvent under reduced pres-

sure, the resulting crude product was puried by silica gel

column chromatography (PhH/AcOEt ¼ 100/0 / 100/4), and

recrystallized from toluene/EtOH to give 21 (1.47 g, 18%) as

a dark purple solid.

Mp: 253–255 ^ꢁC (decomp.). ¹H NMR (400 MHz): d 7.76 (d, J ¼

8.6 Hz, 8H), 7.56 (d, J ¼ 8.6 Hz, 8H), 7.25 (s, 4H), 3.20 (s, 12H),

1.37 (s, 36H). ¹³C NMR (125 MHz): d 181.8, 156.8, 139.2, 136.0,

135.0, 134.5, 127.9, 126.0, 39.2, 35.2, 31.2. IR: 2964, 2871, 1702,

1595, 1477, 1397, 1349, 1333, 1307, 1269, 1217, 1160, 1111,

1085, 1042, 936, 888, 865, 842, 812, 793, 762, 671, 630, 601, 580,

547 cm^ꢀ1. HRMS (FAB) calcd for C₅₈H₆₉N₄O₁₀S₄: 1109.3897 [(M

+ H)⁺]; found: 1109.3899. Anal. calcd for C₅₈H₆₈N₄O₁₀S₄: C,

62.79 H, 6.18; N, 5.05. Found: C, 62.57 H, 6.13; N, 5.00.

Mp: 116–118 ^ꢁC. ¹H NMR (400 MHz): d 11.87 (s, 4H), 7.95 (s,

4H), 7.67 (d, J ¼ 9.1 Hz, 4H), 6.54 (d, J ¼ 9.1 Hz, 4H), 1,60–1.46

(m, 16H), 1.37–1.25 (m, 16H) 0.89 (t, J ¼ 6.7 Hz, 24 H). ¹³C NMR

(125 MHz): d 188.6, 151.5, 137.5, 129.3, 126.1, 122.6, 116.4,

110.6, 51.0, 31.6, 26.9, 26.6, 22.6, 14.0. IR: 3119, 2954, 2929,

2857, 1594, 1554, 1514, 1479, 1405, 1367, 1255, 1217, 1156,

1092, 997, 978, 858, 816, 789, 659, 558 cm^ꢀ1. HRMS (FAB) calcd

for C₈₆H₁₂₈N₈O₁₀S₄Na: 1583.8534 [(M + Na)⁺]; found: 1583.8536.

Anal. Calcd for C₈₆H₁₂₈N₈O₁₀S₄$toluene: C, 66.12 H, 8.26; N,

7.17. Found: C, 66.12 H, 8.40; N, 7.09.

Conﬂicts of interest

There are no conicts to declare.

Acknowledgements

Preparation of 22

This work was partly supported by JSPS KAKENHI Grant

numbers JP17K05769, JP20H04655 and JP20K05442, the Murata

Science Foundation, 2020 Mitsui Chemical Award in Synthetic

Organic Chemistry, Japan, Tobe Maki Scholarship Foundation,

Iketani Science and Technology Foundation, Yamaguchi

Educational and Scholarship Foundation, and the research

program “Dynamic Alliance for Open Innovation Bridging

Human, Environment and Materials” from MEXT, Japan.

A mixture of 20 (4.50 g, 4.27 mmol) and conc. H₂SO₄(100 mL)

was stirred at 100 ^ꢁC. Aer cooling to rt, the mixture was poured

into ice water (ca. 600 mL). The mixture was basied with NaOH

and the resulting precipitate was collected by ltration, washed

with H₂O and dried under vacuum to give a blue solid (5.36 g),

which was used for the next reaction without further purica-

tion. A mixture of the product, 4-(dihexylamino)benzene-

sulfonyl chloride (5.50 g, 18.1 mmol) in pyridine was stirred at

70 ^ꢁC for 40 h. Aer cooling to rt, the solvent was removed under

reduced pressure. The product was dissolved in CHCl₃. The

solution was washed with brine and dried over MgSO₄. Aer

evaporation of the solvent under reduced pressure, the resulting

blue solid was puried by silica gel column chromatography

(PhH/AcOEt ¼ 9/1), followed by recrystallization from toluene/

EtOH to give pure 22 (494 mg, 14% in two steps) as a dark

purple solid.

Notes and references

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Mp: 230–231 ^ꢁC. ¹H NMR (400 MHz): d 13.11 (s, 2H), 7.695 (s,

2H), 7.695 (d, J ¼ 9.2 Hz, 4H), 7.20–6.85 (br s, 4H), 6.63 (s, 2H),

6.55 (d, J ¼ 9.1 Hz, 4H), 3.25 (t, J ¼ 7.6 Hz, 8H), 1.59–1.47 (m,

8H), 1.33 (hext, J ¼ 7.4 Hz, 8H), 0.93 (t, J ¼ 7.4 Hz, 12H). ¹³C

NMR (125 MHz): d 185.0, 151.2, 146.1, 136.3, 129.2, 128.4, 123.8,

123.1, 119.0, 110.5, 108.8, 50.7, 29.1, 20.2, 13.9. IR: 3440, 3290,

2957, 2931, 2870, 1650, 1601, 1571, 1539, 1515, 1472, 1451,

1408, 1381, 1349, 1318, 1298, 1251, 1204, 1179, 1146, 1092, 995,

983, 926, 900, 873, 847, 821, 776, 720, 656, 561, 516, 507, 490,

441 cm^ꢀ1. HRMS (FAB) calcd for C₄₂H₅₄N₆O₆S₂Na: 825.3444 [(M

+ Na)⁺]; found: 825.3450. Anal. calcd for C₄₂H₅₄N₆O₆S₂: C, 62.82

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Preparation of 23

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Article Doi

Color-tunable arylaminoanthraquinone dyes through hydrogen-bond-assisted charge transfer interaction

DOI: 10.1039/d1ra03985g

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