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Electrochimica Acta: Bin Yao, Fengkun Chen, Hong Jiang, Jie Zhang, Xinhua Wan

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Electrochimica Acta 166 (2015) 73–81

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Isomer effect on the near-infrared electrochromism of anthraquinone


imides
Bin Yao a , Fengkun Chen a , Hong Jiang b , Jie Zhang a , Xinhua Wan a, *
a
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and
Molecular Engineering, Peking University, Beijing 100871, China
b
Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering,
Peking University, Beijing 100871, China

A R T I C L E I N F O A B S T R A C T

Article history: To deeply explore the interplay between molecular structure and near-infrared electrochromism of
Received 27 January 2015 anthraquinone imides, two pairs of unsubstituted isomers (Ia and Ib) and nitro-substituted isomers
Received in revised form 5 March 2015 (IIa and IIb) of anthraquinone imides were synthesized, in which the molecules Ia and IIa took more
Accepted 7 March 2015
linear shapes than Ib and IIb. Cyclic voltammetry and spectroelectrochemistry were combined to
Available online 11 March 2015
investigate their electrochemical properties. Cyclic voltammetry showed that Ib and IIb revealed
decreased first reduction potentials and low cyclic stability compared to their isomers, indicating that the
Keywords:
isomerization weakened the stabilization effect. Upon one-electron reduction, both the absorption
Isomer effect
Near-infrared electrochromism
wavelengths and absorption intensities of radical anions were greatly dependent on the structures of
Anthraquinone imide isomers. The radical anions of Ia, IIa, and IIb illustrated NIR absorptions peaked at 820, 1260, and
Structure-property relationship 1380 nm, respectively, but that of Ib exhibited only weak absorption in the visible region centered at
Theoretical calculation 660 nm. Gaussian calculations suggested that the electrons were delocalized over the whole molecular
skeletons of Ia and IIa radical anions, but the effective conjugation length was interrupted on the imide
section in both Ib and IIb. The isomer effects on the effective conjugation length and electron density
distribution were considered to rationalize the different electrochromic behaviors.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction structure-property relationship.[18] With the development of


material science, it is urgent to develop cathodic materials to form
Near-infrared (NIR) electrochromic (EC) materials have been complementary circuits with the available anodic ones. Besides,
attracting considerable attention for their promising applications in cathodic materials can be operated at relatively low voltages,
military and civilian fields [1–4]. Despite the fact that the most which can avoid the degradation problem of materials at high
extensively explored NIR EC materials are inorganic compounds, potentials. Aromatic imides [19–21] and aromatic quinones [22–25]
including transition metal oxides [5,6] and transition metal are two kinds of cathodically active systems that display intense
complexes [7–9], organic EC compounds with NIR absorptions absorptions in the telecommunication wavelength range
are emerging as potential alternatives due to their several (i.e., 1310 and 1550 nm) upon one-electron reduction. For example,
advantages, such as tunable structure, solution-processability, a NIR optical band arising from the excitation of p-electrons along
fast response, and high color contrast ratio [10–12]. Actually, in the stacks appears when reduced naphthalene diimides form
the past decade, a large number of p-type materials, including ordered p-stacks in solution [26] or gel [19]. Concerning the
poly(triarylamine)s [13,14] and conjugated conducting polymers diquinone compounds, the effects of substituent structure, number
[15–17], have been investigated as NIR EC materials. Nevertheless, of quinone motif, and EC mechanism on the radical anionic
in comparison with the well-investigated organic anodically absorptions have also been systematically investigated by Miller
NIR EC materials, cathodically EC materials are relatively less and co-workers [23–25]. However, the tedious synthetic routes and
concerned, mainly owing to the limited number of n-type poor solubilities hamper their further practical applications.
materials, low long-term stability of radical anions, and undefined Recently, a novel kind of cathodically NIR EC materials named
anthraquinone imides (AQIs) [27–34], simultaneously containing
the advantanges of quinone and imide units, were reported by
* Corresponding author. Tel: +86 10 62754187; fax: +86 10 62751708. our group. Unsubstituted AQIs [28] or AQIs substituted with
E-mail address: xhwan@pku.edu.cn (X. Wan). electron-donating groups [32] exhibit intensive NIR absorptions

http://dx.doi.org/10.1016/j.electacta.2015.03.057
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
74 B. Yao et al. / Electrochimica Acta 166 (2015) 73–81

peaked at around 820 nm in their radical anionic states arising spectrometer at ambient temperature with CDCl3 as the solvent.
from p*-p* transitions. The substitution with electronegative Chemical shifts in 1H NMR and 13C NMR were recorded in ppm with
groups remarkably red-shifts the radical anionic absorptions tetramethylsilane as a standard. High-resolution mass spectra
[28,33]. The introduction of AQI chromophores into helical were recorded on a Bruker APEX IV Fourier transform ion cyclotron
polymers [29,34], liquid crystalline compounds [30], and low resonance mass spectrometer. Elemental analyses were performed
molecular mass organic organic gelators [31] demonstrate on an Elementar Vario EL instrument.
interesting electrochemically triggered chiroptical switching UV–vis–NIR absorption spectra were recorded on a Hitachi
properties. However, most of these systems exhibit NIR U-4100 spectrophotometer. The cyclic voltammetry and
electrochromism only at around 820 nm, which is far shorter than differential pulse voltammetry measurements were carried out
the telecommunication wavelength range. It is desired to deeply on a CHI840B electrochemical workstation in CH2Cl2 solutions
understand the structure-property relationship and tune the containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) as
radical anionic absorptions of AQIs. Isomer effect has been known the supporting electrolyte. A three-electrode assembly was used
to possess important influence on the performances of with a platinum disk as working electrode, a platinum wire
photoelectric materials, such as organic solar cells and organic as counter electrode, and a silver wire as pseudo-reference
thin film transistors [35–38]. It functions by affecting the electron electrode. All the experimentally measured redox potentials were
density distributions and the closely related intramolecular or calibrated externally using a solution of ferrocene (Fc/Fc+).
intermolecular interactions. But no work has been reported Spectroelectrochemical measurements were carried out on a
concerning with the isomer effect on the NIR electrochromism Hitachi U-4100 spectrophotometer connected to electrochemical
of AQIs as well as other organic n-type NIR EC materials. workstation in an optical transparent thin layer (OTTLE) cell [41].
To achieve this objective, four AQI derivatives, i.e., Before every electrochemical measurement, the solution was
N-(1-hexylheptyl)anthraquinone-2,3-dicarboxylic imide (Ia), degassed with nitrogen to exclude the trace oxygen.
N-(1-hexylheptyl)anthraquinone-1,2-dicarboxylic imide (Ib),
N-(1-hexylheptyl)-6-nitro-anthraquinone-2,3-dicarboxylic imide 2.3. Computational methods
(IIa), and N-(1-hexylheptyl)-6-nitro-anthraquinone-3,4-dicarbox-
ylic imide (IIb) were synthesized (Chart 1). Among them Ia and Ib, The Gaussian calculations were performed with the Gaussian
IIa and IIb are isomers, respectively. Their electrochemical 09 program package [42]. The geometries of all AQI molecules in
properties were investigated by cyclic voltammetry and spec- both the neutral and radical anionic states were fully optimized
troelectrochemical methods. With the addition of one electron, using Kohn-Sham Density Functional Theory (DFT) based on the
both the absorption wavelengths and absorption intensities varied Becke's three parameter hybrid functional B3LYP with the
a lot between different isomers. Density-functional theory (DFT) 6-31+G(d, p) basis set [43] and followed by vibrational-frequency
and time-dependent DFT (TD-DFT) calculations were performed to calculations to confirm that real minima were obtained. To
rationalize the isomer effect observed. simplify the calculations, the methyl group was employed to
replace the long alkyl chain. For radical anions, the corresponding
2. Experimental spin-unrestricted approach was used. The frontier molecular
orbital (MO) energy levels were calculated based on the optimized
2.1. Materials structures. TD-DFT was employed to simulate the vertical
transitions of the first 10 states at the UB3LYP/6-31+G(d, p) level.
All chemical reagents were of analytical grade and purchased In all cases, the solvation effects were considered using the
from J&K, Aldrich, Acros, and TCI Chemical Co. Dichloromethane polarizable continuum model (PCM) with CH2Cl2 as the solvent. In
(DCM) and N-dimethylformamide (DMF) were dried and distilled addition, the orbital pictures were prepared using GaussView [44].
over CaH2, and stored over 0.4 nm molecular sieves prior to use.
Other chemicals were used without further purification. 2.4. Synthesis
9,10-Anthraquinone-2,3-dicarboxylic anhydride [27], 9,10-anthra-
quinone-1,2- dicarboxylic acid [39], and N-(1-hexylheptyl)amine 2.4.1. N-(1-hexylheptyl)anthraquinone-2,3-dicarboxylic imide (Ia)
[40] were prepared according to the reported procedures. 9,10-Anthraquinone-2,3-dicarboxylic anhydride (0.28 g,
6-Nitro-9,10-anthraquinone-dicarboxylic anhydrides were 1.0 mmol), anhydrous DMF (12 mL), and N-(1-hexylheptyl)
synthesized with the published procedure of 6-nitro-9,10- amine (0.22 g, 1.1 mmol) were successively added into a 50 mL
anthraquinone-2,3-dicarboxylic anhydride [28]. three-necked flask under nitrogen. After stirring for 1 h at room
temperature, the mixture was heated to reflux for 4 h. After cooling
2.2. Characterizations to room temperature, the solution was poured into a dilute
hydrochloric acid solution (100 mL). The precipitated solids
1
H NMR, 13C NMR, and heteronuclear multiple bond coherence were filtrated and washed with methanol. After drying, the
(HMBC) spectra were measured on a Bruker AVANCE III (400 MHz) product was purified by chromatography (silica gel, petroleum

O O
O O O
O

N R N R
O O 2N O
O 2N
O O O N
O O N O
O O R
R
Ia Ib IIa IIb
R: 1-hexylheptyl
Chart 1. Chemical structures of four AQI molecules.
B. Yao et al. / Electrochimica Acta 166 (2015) 73–81 75

ether/dichloromethane = 1/1, v/v) to afford Ia (0.25 g) in 55% yield. (100 MHz, CDCl3) d/ppm: 181.7, 180.9, 166.7, 164.5, 138.6, 138.2,
1
H NMR (400 MHz, CDCl3) d/ppm: 8.77 (d, J = 0.92 Hz, 2H), 8.37 135.0, 134.4, 134.3, 133.4, 132.5, 132.3, 131.1, 127.8, 127.2, 127.0, 53.5,
(m, 2H), 7.88 (m, 2H), 4.31–4.22 (m, 1H), 2.17–2.05 (m, 2H), 32.4, 31.7, 28.7, 26.7, 22.6, 14.0. HRMS (ESI positive): m/z calcd for
1.80–1.68 (m, 2H), 1.36–1.14 (m, 16H), 0.85 (t, J = 7.0 Hz, 6H). C29H34NO4 [M+H]+: 460.2488; found: 460.2493. Elemental
13
C NMR (100 MHz, CDCl3) d/ppm: 181.5, 166.9, 138.0, 135.6, 134.8, analysis calcd (%) for C29H33NO4: C 75.79, H 7.24, N 3.05; found:
133.1, 127.7, 122.4, 53.2, 32.3, 31.7, 28.9, 26.6, 22.5, 14.0. HRMS (ESI C 75.66, H 7.05, N 3.03.
positive): m/z calcd for C29H34NO4 [M+H]+: 460.2488; found:
460.2482. Elemental analysis calcd (%) for C29H33NO4: C 75.79, 2.4.3. N-(1-hexylheptyl)-6-nitro-anthraquinone-2,3-dicarboxylic
H 7.24, N 3.05; found: C 75.76, H 7.24, N 3.03. imide (IIa) and N-(1-hexylheptyl)-6-nitro-anthraquinone-3,4-
dicarboxylic imide (IIb)
2.4.2. N-(1-hexylheptyl)anthraquinone-1,2-dicarboxylic imide (Ib) 6-Nitro-9,10-anthraquinone-dicarboxylic anhydrides (three
9,10-Anthraquinone-1,2-dicarboxylic acid (0.60 g, 2.0 mmol) isomers) were synthesized as mixtures from 4-nitrophthalic
and acetic anhydride (20 mL) were added to a 50 mL round anhydride as a starting material [28].
bottom flask. The mixture was heated to reflux for 2 h, and cooled 6-Nitro-9,10-anthraquinone-dicarboxylic anhydrides (three
to room temperature, and then yellow crystalline solids were isomers, 0.52 g, 1.6 mmol), N-(1-hexylheptyl)amine (0.37 g,
precipitated. The solid was filtrated and washed with petroleum 1.8 mmol), and dry DMF (20 mL) were added to a 50 mL
ether to obtain 9,10-anthraquinone-1,2-dicarboxylic anhydride three-necked round bottom flask under nitrogen. After stirring
(0.48 g, yield 86%) with no further purification. for 1 h at room temperature, the mixture was heated to reflux for
9,10-Anthraquinone-1,2-dicarboxylic anhydride (0.28 g, 4 h. Then, the mixture was allowed to cool to room temperature,
1.0 mmol), N-(1-hexylheptyl)amine (0.22 g, 1.1 mmol), and anhy- and poured into a dilute hydrochloric acid solution (100 mL).
drous DMF (12 mL) were added into a 25 mL three necked flask The solids thus precipitated were filtrated and washed with
under nitrogen. After stirring for 1 h at room temperature, the methanol. After drying, the crude product was purified by column
mixture was heated to reflux for 4 h. After cooling to room chromatography (silica gel, petroleum ether/dichloromethane =
temperature, the solution was poured into a dilute hydrochloric 1/1, v/v). IIa (Rf = 0.50, 80 mg, yield: 10%) and IIb (Rf = 0.45, 121 mg,
acid solution (50 mL). The solids thus precipitated were filtrated yield: 15%) could be obtained at the same time.
and washed with methanol. After drying, the product was purified IIa: 1H NMR (400 MHz, CDCl3) d/ppm: 9.17 (d, J = 2.2 Hz, 1H),
by chromatography (silica gel, petroleum ether/dichloromethane = 8.83 (s, 1H), 8.80 (s, 1H), 8.67 (dd, J1 = 8.5 Hz, J2 = 2.2 Hz, 1H), 8.58
1/3, v/v) to afford Ib (0.23 g) in 50% yield. 1H NMR (400 MHz, (d, J = 8.5 Hz, 1H), 4.32–4.23 (m, 1H), 2.17–2.05 (m, 2H), 1.80–1.68
CDCl3) d/ppm: 8.75 (d, J = 7.8 Hz, 1H), 8.35 (dd, J1 = 7.0 Hz, J2 = 1.6 (m, 2H), 1.36–1.14 (m, 16H), 0.85 (t, J = 7.0 Hz, 6H). 13C NMR
Hz,1H), 8.30 (dd, J1 = 7.0 Hz, J2 = 1.6 Hz,1H), 8.23 (d, J = 7.8 Hz, 1H), (100 MHz, CDCl3) d/ppm: 180.2, 179.8, 166.5(d), 151.6, 137.7, 137.5,
7.86 (m, 2H), 4.35–4.25 (m, 1H), 2.17–2.05 (m, 2H), 1.80–1.68 136.4, 136.2(d), 134.2, 129.7, 128.7, 123.0, 122.8(d), 53.4, 32.3, 31.6,
(m, 2H), 1.36–1.14 (m, 16H), 0.85 (t, J = 7.0 Hz, 6H). 13C NMR 28.9, 26.6, 22.5, 14.0. HRMS (ESI positive): m/z calcd for C29H33N2O6

Scheme 1. Syntheses of AQI derivates Ia,Ib, IIa, and IIb.


76 B. Yao et al. / Electrochimica Acta 166 (2015) 73–81

Fig. 1. (a) CVs recorded in CH2Cl2 solutions (1 mM) at a scanning rate of 100 mV/s; (b) DPVs of four molecules in CH2Cl2 solutions; (c) 24 repeated CV cycles of Ib in its first
reduction state; (d) 24 repeat CV cycles of IIb in its first reduction state. The black arrows in every figure indicate the scanning directions, the starting points are the lower
potentials (less negative). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

[M+H]+: 505.2339; found: 505.2344. Elemental analysis calcd (%) for were obtained via a modified method requiring no isolation of
C29H32N2O6: C 69.03, H 6.39, N 5.55; found: C 69.24, H 6.47, N 5.41. isomers before final imidization (for the possible isomeric
IIb: 1H NMR (400 MHz, CDCl3) d/ppm: 9.16 (d, J = 2.0 Hz, 1H), structures of each step, see Scheme S1).
8.79 (d, J = 7.8 Hz, 1H), 8.64 (dd, J1 = 8.5 Hz, J2 = 2.0 Hz,1H), 8.52 (d, Two pure isomers could be gained simultaneously by
J = 8.5 Hz, 1H), 8.30 (d, J = 7.8 Hz, 1H), 4.36–4.27 (m, 1H), 2.17–2.05 elaborative column chromatography. The eluent with
(m, 2H), 1.80–1.68 (m, 2H), 1.36–1.14 (m, 16H), 0.85 (t, J = 7.0 Hz, Rf = 0.50 was confirmed to be IIa by comparing with the reported
6H); 13C NMR (100 MHz, CDCl3) d/ppm: 180.4, 178.9, 166.3, data. The chemical structure of the other one with Rf = 0.45 was
164.1,151.7, 138.7, 138.1, 135.7, 135.5, 133.9, 131.9, 131.5, 129.3, characterized by 1H NMR (Fig. S1), 13C NMR (Fig. S2), and HMBC
128.3, 127.7, 123.2, 53.5, 32.3, 31.7, 28.9, 26.7, 22.5, 14.0. HRMS (ESI spectra (Fig. S3). As illustrated in Fig. S3, only 3JC-H correlation of
positive): m/z calcd for C29H33N2O6 [M+H]+: 505.2339; found: the proton Ha to the carbon C1 was observed, and no additional
505.2340. Elemental analysis calcd (%) for C29H32N2O6: C 69.03, H correlation to C1 was detected, indicating an expected structure.
6.39, N 5.55; found: C 69.15, H 6.55, N 5.33. Mass spectroscopy and elementary analysis gave consistent
results. Unfortunately, we failed to obtain the third isomer IIc
3. Results and discussion by column chromatography and HPLC due to the relatively low
content and nearly identical Rf value to IIb.
3.1. Synthesis
3.2. Electrochemical properties
The synthetic route of four AQI derivates is shown in Scheme 1.
Ia and Ib were gained as pure substances according to the literature Cyclic voltammetry was firstly explored to examine the redox
method [27,39]. The synthesis of IIa was reported previously [28]. properties of these isomeric molecules. The cyclic voltammograms
Nevertheless, the repeated recrystallizations employed to separate (CVs) and corresponding differential pulse voltammograms (DPVs)
isomers before the oxidation reaction greatly reduce synthetic are illustrated in Fig. 1 and Figs. S4–S5. The corresponding redox
yield and only one pure isomer is obtained. In this work, IIa and IIb potentials as well as electron affinity (EA) are summarized in Table 1.

Table 1
Redox potentials, corresponding EAs, and maximum absorption wavelengths of four AQI derivates.

Entry E1/21 (V)a E1/22 (V)a Found EA (eV)b Calculated ELUMO (eV)c Calculated EHOMO (eV)c lmax (nm)d
e e
Ia 1.07 (1e) 1.51 (1e) 4.03 3.71 7.70 820
Ib 1.21 (1e) 1.45 (1e) 3.89 3.46 7.50 660
IIa 0.84 (1e) 1.28 (1e) 4.26 4.03e 7.97e 1260
IIb 0.97 (1e) 1.41 (1e) 4.13 3.90 7.72 1380
a
Only the first two reduction potentials are listed, determined in CH2Cl2/ TBAP (0.1 M) with ferrocene used as internal reference, c = 1 mM, n = 100 mV/s.
b
Found EA =  (E1/21 + 5.1) (eV) [45,46].
c
Calculated EHOMO and ELUMO values were obtained from Gaussian calculations at the B3LYP/6-31+G(d, p) level.
d
Only the observed maximum of the longest wavelength in the radical anionic states are listed.
e
Values from reference [33].
B. Yao et al. / Electrochimica Acta 166 (2015) 73–81 77

Fig. 1a illustrates the CVs of four molecules. Each main redox 3.3. Spectroelectrochemistry
couple was one-electron reduction, deduced from the relative
proportion of each reduction process in the DPVs of these Spectroelectrochemical measurements were subsequently
molecules (Fig. 1b). The peak current of first reduction process carried out in CH2Cl2 solutions to investigate the structure-property
was proportional to the square root of scan rate (Fig. S4), indicating relationship between the molecular structures and EC properties
a diffusion-controlled redox process in solution. of AQI derivatives. In the neutral state, no molecule showed
As shown in Table 1, the first reduction potentials of Ib and IIb absorption bands beyond 400 nm (Fig. S6), and the solutions were
are 1.21 V and 0.97 V, respectively, being more negative than nearly colorless transparent. However, when an electron was
those of Ia and IIa. It implied that it was much more difficult for added, both absorption wavelength and absorption intensity were
Ib and IIb to get an electron, an indicative of the weakened found to be greatly dependent on the structures. The UV–vis–NIR
stabilization effect of molecules due to the distorted structures. Ia spectra of four molecules corresponding to their first reduction
revealed two redox couples, which could be attributed to the states under external voltages are displayed in Fig. 2, and the
reduction of two quinone units since a quinone accepts an electron maximum absorption wavelengths (lmax) of their radical anions
more easier than an imide [47,48]. In contrast, more than two are listed in Table 1.
redox couples were observed for Ib, probably due to the presence of For Ia, a strong NIR absorption band peaked at 820 nm gradually
some irreversible reduction processes arising from the distorted increased under 1.1 V (Fig. 2a), and this phenomenon was
structure as in the reduction of some imides [49]. The DPV at 1.65 V consistent with our previously published results [28]. By compari-
(Fig. 1b) and CVs at a low scanning rate (25 mV/s, Fig. S4c) of son, it could also be found that the alkyl chains on the imide group
Ib further confirmed the existence of irreversible reduction did not affect the EC properties too much since the alkyl chains were
processes. In the case of IIa and IIb, with the introduction of not involved in redox processes. Interestingly, the electrochromism
electronegative nitro group, both IIa and IIb displayed three of Ib was greatly different from Ia, with only weak absorption bands
one-electron redox couples. Besides, the reversibility of the third covering the visible region was observed under 1.2 V (Fig. 2b).
reduction process of IIb was not good since the potential Besides, in the process of measurement, we found that the EC
splitting (210 mV) between reduction and oxidation direction stability of Ib was low since it was very easy to be over reduced or
was relatively large at the same scanning rate (100 mV/s). Moreover, deteriorated on the electrode surface. This low EC stability was in
nitro-substituted IIa and IIb demonstrate higher first reduction line with the above cyclic voltammetry results that the redox
potentials, which are in consistent with the published results potential splitting DE between first and second oxidation process
that electron-withdrawing groups make reduction easier to was small and the cyclic voltammetry stability of Ib was pretty poor.
occur [33]. The EC properties of Ia and Ib illustrated that the imide moiety
Furthermore, the cyclic stability of first reduction process of at 1, 2 position of AQI blue-shifted the radical anionic absorption.
molecules was characterized using cyclic voltammetry (Figs. 1c–d, However, it was not the case for the other isomers with nitro-
Fig. S5). With increasing number of cycles corresponding to substituent. Upon one-electron reduction, two NIR absorption
the first reduction state, Ib (Fig. 1c) and IIb (Fig. 1d) exhibited bands were observed on both IIa and IIb. The IIa radical anions
decreased stability, while Ia (Fig. S5a) and IIa (Fig. S5b) showed strong NIR absorption bands peaked at 880 and 1260 nm
showed good cyclic stability. It meant that the distorted structures (Fig. 2c), and the IIb radical anions displayed two NIR bands
of Ib and IIb not only reduced the first reduction potentials, but centered at 970 and 1380 nm (Fig. 2d), respectively. Despite
also reduced the redox stability. relatively weak in intensity, the two absorption bands of IIb radical

Fig. 2. UV–vis–NIR spectra of Ia (a), Ib (b), IIa (c), and IIb (d) under different potentials in CH2Cl2 solutions.
78 B. Yao et al. / Electrochimica Acta 166 (2015) 73–81

Fig. 3. Optimized geometries, dipole moments, and energy orbitals of molecules in their neutral states at the B3LYP/6-31+G(d, p) level.

anion were found to be slightly red-shifted in comparison with adopt completely planar structures. While for their corresponding
those of IIa, distinct to those of Ia and Ib. isomers Ib and IIb, the imide groups deviated from the molecular
It should be noted that the absorption spectra in their dianionic skeletons due to the large steric hindrance between two adjacent
states did not differ too much (Fig. S7). Additionally, all molecules C¼O double bonds from quinone and imide units. As a
showed relatively poor stability in their dianionic states. The consequence, the twisted and nonplanar molecular structures
corresponding vis–NIR absorption bands would decay if the exerted a great influence on both the dipole moments and energy
applied voltages were maintained. This might be explained by orbitals. As illustrated in Fig. 3, the magnitude of the dipole
the decomposition of the molecules on the electrode. moment of Ib was smaller than that of Ia, but the inclined direction
The above results suggested that both the position of imide meant great symmetry differences in the electron distributions.
moiety and nitro-substituent significantly impacted the EC The dipole moment of IIb was larger than that of IIa, suggesting a
properties in their radical anionic states, including both absorption more effective charge separation in IIb. Corresponding to the
wavelengths and absorption intensities. The role of nitro-substituent difference in the dipole moment, the HOMO orbitals of Ib and IIb
has beenwell-defined, but the effects of the position of imide group is were highly asymmetric, and the electron in the LUMO orbitals of
unclear. Obviously, a subtle balance between these two factors would Ib and IIb was not delocalized onto the imide groups, thus leading
have a decisive effect on the EC properties of molecules. to smaller effective conjugation lengths and weaker delocalization
energies. It would explain the more negative first reduction
3.4. Theoretical calculations in the neutral states potentials of Ib and IIb than those of Ia and IIa. Incidentally, the
calculated LUMO energy levels were in good agreement with
To get a deep insight into the comprehensive effects of various the change trend of experimentally found EAs (Table 1).
factors on the electrochemical and spectroelectrochemical prop-
erties, Gaussian simulations were performed to help expalin the 3.5. Theoretical calculations in the radical anionic states
experimental observations at the molecular level.
The calculated results in the neutral state, including optimized Afterwards, an extra eletron was then added to each molecule,
geometries, dipole moments, and energy orbitals, are shown in and the DFT calculations were carried out in their radicals anionic
Fig. 3. First inspection of the optimized geometries, both Ia and IIa states. The corresponding calculated results are illustrated in Fig. 4.

Fig. 4. Optimized geometries, dipole moments, frontier molecular orbitals, and orbital energies of the radical anions simulated at the UB3LYP/6-31+G(d, p) level: (a) Ia and Ib;
(b) IIa and IIb.
B. Yao et al. / Electrochimica Acta 166 (2015) 73–81 79

Fig. 5. UV–vis–NIR spectra of Ia, Ib, IIa, and IIb in their radical anionic states in CH2Cl2 solutions: (a) experimental results; (b) calculated results.

Based on the optimized strutures, TD-DFT were also done, and the observed different orbital transitions explained the blue-shifted
simulated absorptions as well as detailed electron transitions are effect of isomer compared Ib radical anion with that of Ia.
displayed in the Fig. 5, Table 2, and Table S1. As shown in Fig. 5, In respect to IIa and IIb radical anions, the red-shift effect of
compared the experimental findings with calculated results, the electro-withdrawing nitro-substituent is obvious and has been
calculated absorptions of four molecules were approximately in reported [28]. Meanwhile, the position of imide group also plays
consistent with our experimental observations apart from the a profound role in determining the EC characteristics of
relative intensities of two simulated absorption bands of IIa radical molecules. As shown in Fig. 4b, the electron density of IIa
anion differed from the experimental results. More structural and radical anion was delocalizd over the whole molecule skeleton
electronic insights into the results will be detailedly discussed in including the imide moiety in both SOMO(a) and LUMO(a)
the following text. orbitals. However, the electron distribution of the SOMO(a)
As shown in Fig. 4, after getting an electron, the planarity of orbital of IIb radical anion was similiar with Ib that imide group
molecules remained almost unchanged, but the dipole moments did not take part in effective delocalization, and the electron
of all molecules slightly increased, indicating more charge density of LUMO(a) was inclined to distribute along the
separations in their radical anionic states. In addition, the dipole electron-withdrawing side of nitro-substituent and imide
moments of Ib and IIb radical anions were much larger than groups. The observed lmaxs of IIa and IIb were both attributed
those of Ia and IIa, implying more charge separations in Ib and IIb to SOMO(a) ! LUMO(a) transitions (Table 2 and Table S1).
radical anions. The differences in charge separations would have a Though weak in intensity, the calculated lmax of IIb radical anion
decisive influence on the electron distributions and electron was relatively red-shifted than that of IIa, being in accordance
transfer processes. with the experimental finding. The high-lying molecular orbitals
For Ia and Ib radical anions, the imide groups play critical roles and instability of system might be responsible for the red-shift
in determining the electron distributions. The electron in the absorptions.
singly occupied molecular orbital (SOMO(a)) of Ib radical anion Overall, the nonplanar structures of Ib and IIb reduced the
was not delocalized onto the imide group because of the steric effective conjugation lengths and the molecular delocalization
hindrance. The differences of LUMO(a) orbitals were even more energies, and consequently resulted in relatively higher molecular
significant than those of SOMO(a) orbitals. The electron was only energy levels in both the neutral and the radical anionic states.
delocalized onto the side of imide group of Ib radical anion, Moreover, the greatly different molecular orbital symmetries of Ib
while on the contrary the electron was delocalized over the and IIb radical anions depressed the probability of electron
entire molecule of Ia radical anion. The observed lmax of Ia transitions, and therefore the corresponding radical anionic
radical anion was the superposition of SOMO(a) ! LUMO(a) and absorption intensities were relatively weaker than those of Ia
SOMO(a) ! LUMO + 1(a) transitions because of the similar and IIa.
excitation energies (Table S1). Nevertheless, the observed lmax
of Ib radical anion was ascribed to the SOMO(a) ! LUMO + 1(a) 4. Conclusions
transition due to the low oscillator strength (f = 0.008) of
SOMO(a) ! LUMO(a) transition (Table 2). Therefore, these Two pairs of unsubstituted (Ia and Ib) and nitro-substituted
AQI isomers (IIa and IIb) were successfully synthesized to
Table 2 investigate isomer effect on their EC properties. Ib and IIb
Calculated radical anionic absorptions together with excitation energies (DE), showed more negative first reduction potentials and low cyclic
oscillator strengths (f), and dominant transitions of Ib and IIb at the UB3LYP/6-31+G voltammetry stability, suggesting less delocalization energy of
(d, p) level.
their twisted structures. Upon reduction to radical anionic
Sn DE (eV, nm) f Dominant transitions (%) states, Ib showed only weak visible electrochromism. Both IIa
Ib and IIb radical anions illustrated two NIR absorption bands, and
S1 0.65, 1906 0.008 S(a) ! L(a) (99%) IIb radical anion showed slightly red-shifted absorptions with
S2 2.00, 619 0.111 S(a) ! L + 1(a) (95%) decreased intensity. Gaussian calculations indicated that the
S3 2.38, 522 0.115 S(a) ! L + 2(a) (94%)
nonplanar structures together with the molecular dipole moments
IIb
S1 0.85, 1462 0.015 S(a) ! L(a) (82%), S(a) ! L + 1(a) (17%) of Ib and IIb were the essential factors of isomer effect. The steric
S2 1.14, 1088 0.223 S(a) ! L + 1(a) (82%), S(a) ! L(a) (17%) hindrance between two adjacent C¼O double bonds led to the
S3 2.35, 527 0.030 S(a) ! L + 2(a) (70%), S(a) ! L + 3(a) (22%) nonplanar structures of Ib and IIb, and the nitro-substituent and
S5 2.55, 487 0.033 S(a) ! L + 3(a) (74%), S(a) ! L + 1(a) (19%) the position of imide group together determined the molecular
*S and L refer to SOMO and LUMO orbitals; a refers to spin direction. molecular dipole moments as well as the electron distributions.
80 B. Yao et al. / Electrochimica Acta 166 (2015) 73–81

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