Dyes and Pigments 206 (2022) 110613

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Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

A near-infrared absorbing ring-fused quinoid-bisboron pyrrole dye with

double BF2 chelation
Yue Liang a, 1, Dongxiang Zhang a, 1, Jie Wang b, 1, Meiheng Lv a, Feng Yan a, Zhangrun Xu b,
Jianjun Du c, **, Xin-Dong Jiang a, *
a
Liaoning & Shenyang Key Laboratory of Functional Dye and Pigment, Shenyang University of Chemical Technology, Shenyang, China
b
Department of Chemistry, College of Sciences, Northeastern University, Shenyang, China
c
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China

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

Keywords: Ring-fused quinoid-bisboron pyrrole dyes with double BF2 chelation (QBBP) were prepared for the first time.
Near-infrared According to X-ray crystallographic analysis, the centrosymmetric structure of QBBP was confirmed. The core of
Quinoid-bisboron the central quinone moiety and two ring-fused pyrroles is almost planar, and the arrangement of aggregates
Pyrrole
involve J-type packing. Bisboron dye QBBP underwent two successive one-electron reduction and two successive
Dye
one-electron oxidation processes. QBBP absorbs in the near-infrared (NIR) with a high molar extinction coef­
J-aggregate
ficient. Although QBBP shows no fluorescence and low intersystem crossing (ISC) efficiency, it has considerable
photothermal conversion efficiency and is desirable for a photothermal-photodynamic therapy agent.

1. Introduction quinolone-based diboron complex, BPh2-type dyes become popular in

the quinoid bisboron system (Fig. 1d and e) [34–37]. Nevertheless, such
Since near-infrared (NIR) absorbing (λabs > 650 nm) dyes, which BPh2-type quinoid bisboronpyrrole dyes were found to have a short
possess low side effects, deep penetration, etc. [1–3], play vital roles in wavelength (Fig. 1e). Therefore, it was a challenge to synthesise the
array of applications, such as heat absorbers, optical filters, NIR-absorbing BF2-type QBBP dyes (Fig. 1f). Our group recently focused
information-storage materials, bioimaging, photothermal and photo­ on the unique ring-fused pyrrole and NIR absorbing
dynamic therapies; such dyes are highly sought after [4–6]. Conse­ BODIPYs/aza-BODIPY dyes, and this firmly paved the avenue for us to
quently, to shift the absorption spectra of conventional chromophores explore this topic [38–42]. Additionally, based on relatively low cost
into the NIR region, the extension of π-conjugated systems are the and green synthesis, the ring-fused pyrrole was herein employed to
introduction of donor-acceptor system (D-A) are the key strategies undertake one-pot synthesis of the target dye QBBP with double BF2
[7–17]. NIR absorbing dyes, such as azo dyes, cyanine dyes, rylene chelation for the first time. Furthermore, the structure and nature of
diimides, phthalocyanines, squaraine dyes, and quinone dyes possess QBBP are discussed in detail.
multiple ring fusions [18–23]. However, the difficulty of synthesizing
multiple ring strictures was found to obstruct their widespread appli­ 2. Results and discussion
cation (see Table 1).
Among a variety of chromophores, the unique BR2-type (R = F, Ph) 2.1. Synthesis and structure of symmetric QBBP with double BF2 groups
complex as a typical chromophore has been attracting increasing
attention [24–28]. Especially, dimers which are combined with a linking Aryl-fused pyrroles [13,43,44] with the alkyl chain (–CH2-CH2–)
segment, such as diketopyrrolopyrrole and quinone, efficiently extended reacted with 1,4-benzoquinone to produce the ring-fused dyes QBBP-H
the π-conjugated system to shift their absorption spectra into the NIR and QBBP-OMe in presence of BF.3Et2O (Scheme 1), comparing to the
window (Fig. 1) [29–33]. Due to the unstable character of reported dye QBBP with double BPh2 groups using the corresponding

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (J. Du), [email protected] (X.-D. Jiang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.dyepig.2022.110613
Received 15 June 2022; Received in revised form 25 July 2022; Accepted 25 July 2022
Available online 9 August 2022
0143-7208/© 2022 Elsevier Ltd. All rights reserved.
Y. Liang et al. Dyes and Pigments 206 (2022) 110613

Table 1 dihedral angles were 18.5◦ and this phenyl group of the symphysic ring
Optical properties of QBBP dyes in CH2Cl2 at 298 K. is twisted upwards, and another corresponding phenyl group is twisted
Dye λabs (nm) FHWM(nm) ε [M− 1
cm− 1] downward (Fig. 2b). Moreover, there are two types of intramolecular
interactions, including C–H⋯F (2.2958 (11) Å, 2.4659(12) Å) within the
QBBP-H 718 122 139000
QBBP-OMe 767 152 165000 radius of van der Waals force [45–47]. Thereupon, QBBP-OMe bearing
the ring-fused pyrrole is probably stabilized by the weak force described
above and could be steadily synthesized, compared to the failure of the
reagent BPh3 (Fig. 1e) [34–37]. Regretfully, the corresponding dyes synthesis of NQBBP-H and NQBBP-OMe (Scheme 1). While dye
NQBBPs without the –CH2-CH2– chains were not obtained (Scheme 1), QBBP-OMe adopts coplanar inclined arrangement of its transition
probably owing to the rotation of the aryl group hindering the formation dipole, a slip angle of 40◦ is clearly observed. This arrangement of
of the H⋯F hydrogen bonds (seeing the following Figs. 2b and S1). To aggregate is in great agreement with Kasha’s molecular exciton model,
the best of our current knowledge, this is the first case of p-benzoquinoid and corresponds to textbook cases of J-type (θ < 54.7◦ ) packings for
dye with double BF2 chelation. Notably, according to the 1H NMR QBBP-OMe (Fig. 2c) [48–50].
spectrum of QBBP-OMe, the distinct singlet for the hydrogen atoms of
the benzoquinoid group (δ = 6.83 (s, 2H) ppm) clearly confirmed this
2.2. Optical and photophysical properties
structure (Seeing ESI), which is in great agreement with that of the re­
ported BPh2-type QBBP (Fig. 1e) [32].
There remains a clear need for a deep understanding of the spectral
Moreover, according to an X-ray crystallographic analysis, the
properties of the new dyes QBBP. Owing to the extension of the π-π
centrosymmetric structure of QBBP-OMe was clearly confirmed (Fig. 2).
conjugated system, it is therefore surprising that the absorption maxima
The core consisting of the central quinone moiety and two ring-fused
of dyes QBBP-H and QBBP-OMe in CH2Cl2 are located at 718 and 767
pyrroles is almost planar (Fig. 2a). However, the C2–C1–C10–N1
nm in the NIR region, respectively. NIR dye QBBP-OMe has a wider full

Fig. 1. Design strategies for NIR absorbing dye QBBP bearing with double BF2 chelation.

Scheme 1. Synthesis of NIR absorbing dyes QBBPs with double BF2 chelation.

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Y. Liang et al. Dyes and Pigments 206 (2022) 110613

Fig. 2. Oak ridge thermal ellipsoid plot (ORTEP) views of QBBP-OMe (displacement ellipsoids at the 30% probability level). a) Front; b) top views of the molecular
structure; c) Packing diagram of QBBP-OMe.

width at half maxima (FWHM: 152 nm), comparing to that (122 nm) of 2.3. MO calculations
QBBP-H. Moreover, they possess high molar extinction coefficients
(165000 M− 1 cm− 1 for QBBP-OMe; 139000 M− 1 cm− 1 for QBBP-H) Next, we employed MO calculations to gain insight into QBBP-OMe
(Table S1). However, no fluorescence was observed for them, due to and NQBBP-OMe, although NQBBP-OMe could not be obtained. Based
competitive non-radiative decay, which mainly containing the increased on density functional theory (DFT) and time-dependent density func­
internal conversion. Additionally, since the crystal structure of QBBP- tional theory (TDDFT) methods [53–55], the energy difference between
OMe is determined to be J-aggregate (Fig. 2c), this experimental result is HOMO and LUMO in QBBP-OMe is 1.137 eV, which is less than the
also in great agreement with the no emission of J-aggregate in solvent corresponding value of NQBBP-OMe is 1.176 eV, which is consistent
[51,52]. with the empirical value of the absorption maxima, according to their

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2.5. Singlet oxygen generation ability

Subsequently, we have further insight into singlet oxygen (1O2)

generation of QBBP-H. By using a 150 W xenon lamp at 0.5 mW cm− 2,
QBBP-H in toluene were irradiated with monochromatic light at 730
nm. A commercial 1O2 probe, 1,3-diphenylisobenzofuran (DPBF), was
employed as an indicator, and the efficiency of 1O2 generation was
estimated by detecting the decrease of DPBF absorbance at 418 nm
(Fig. 6a). Based on the linear relationship of the decay curves (Fig. 6b),
the 1O2 yield of QBBP-H was extremely low and calculated to be 0.03,
which are slightly higher than that (0.02) of the typical tetraphenyl aza-
BODIPY [57]. The absorption maximum of QBBP-H was unchanged
during optical radiation, indicating QBBP-H is photostable under light
irradiation. In terms of the calculation formula, one can find that ISC
(kISC) rate is closely related to singlet-triplet energy differences (ΔEst)
[58–60]. Hence, for estimating the difficulty of the ISC, we further
gained insight into the energy gap ΔEst between S1 and T1 state. As listed
in Table S2, the lowest-lying singlet and triplet transitions of QBBP-H
were calculated. Evidently, the energy gap ΔEst between S1 and T1 state
Fig. 3. Normalized absorption spectra of QBBP-H (black curve) and QBBP- is about 1.16 eV [58–60], which is not a favorable energy difference for
OMe (red curve) in CH2Cl2 at 298 K. ISC in QBBP-H system.

structures. It can be seen from the rotation energy barrier (5.7 kcal/mol) 2.6. Photothermal performance
of the phenyl group in NQBBP-OMe that, such small energy barriers
promise its free rotation in solution [42,56], so there is no chance for the The photothermal property of QBBP-H in THF was investigated
intermolecular force like the C–H⋯F bonds in QBBP-OMe to form (Fig. 7). Using a 690 nm laser as a light source, a NIR camera is employed
(Fig. 2b). These MO calculations further illustrated the reason why to measure the temperature change during the optical radiation process
NQBBP-OMe cannot be synthesized. (Fig. 7a). Under different concentrations and power densities, the so­
lution temperatures were found to be gradually enhanced along with the
increment of solution concentrations and optical densities (Fig. 7a and
2.4. Cyclic voltammogram b), indicating that the photothermal properties are concentration and
power dependent. To measure the photothermal conversion efficiency of
Furthermore, the cyclic voltammograms of QBBP are shown in Fig. 5 QBBP-H, a 10 min heating curve was recorded for QBBP-H (30 μM)
and Fig. S2. Bisboron complex QBBP-OMe underwent two successive under 690 nm laser irradiation at a power density of 0.60 W cm− 2
one-electron reduction processes at E1/2 = − 0.144 and − 1.242 V (vs Fc/ (Fig. 7c). Then, we removed the irradiation and recorded a cooling time
Fc+), and two successive one-electron oxidation processes at E1/2 = 1.75 plot versus a negative natural logarithm of the temperature, as revealed
and 2.51 V (vs Fc/Fc+). These results infer the formation of either a in Fig. 7d (τ = 217 s). To measure the photothermal conversion effi­
stable aromatic dianion or dication of the bisboron complex under the ciency (η) [61], the calculated value of QBBP-H was 41%. In addition, as
applied conditions (Fig. S3), owing to many resonators of the limit shown in Fig. S4, QBBP-H has good photothermal stability and can be
structure of charge separation, which may also enhance the stability. recycled as a desirable photothermal reagent.
Both processes remained electrochemically reversible. It was interesting
to note that the energy gap between HOMO and LUMO localized on the
QBBP-OMe is 1.89 V, which was similar to that of the MO calculations
by Matsui et al. (Fig. 1e) [35].

Fig. 4. a) Frontier molecular orbitals of QBBP-OMe (LUMO/HOMO (eV) = -2.904/-4.041) and NQBBP-OMe (LUMO/HOMO (eV) = -3.009/-4.185); b) Potential
energy curves of NQBBP-OMe along the rotation of the (p-OMe)phenyl group. The scan process covers 180◦ rotation divided into 6 steps.

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showed an obvious state of death, while the other three groups of cancer
cells grew well. Therefore, it can be determined that QBBP-H could
generate heat to effectively kill the cancer cells under irradiation, while
the dark toxicity is negligible. Thereupon, according to intracellular
phototherapeutic experiments, QBBP-H has good biocompatibility, low
dark-toxicity, and ability of effectively killing cancer cells.

3. Conclusions

We have successfully synthesized ring-fused quinoid-bisbor­

onpyrrole dyes QBBP-H and QBBP-OMe with double BF2 chelation for
the first time. Based on an X-ray crystallographic analysis, the centro­
symmetric structure of QBBP-OMe was confirmed. The core consisting
of the central quinone moiety and two ring-fused pyrroles is almost
planar, and the arrangement of J-type aggregate packing. QBBP-OMe
with the ring-fused pyrrole is stabilized by the weak force of intra­
molecular interactions (C–H⋯F) and could be steadily synthesized,
comparing to the failure of synthesizing NQBBP. QBBPs are NIR
absorbing with high molar extinction coefficients. Bisboron complex
QBBP underwent two successive one-electron reduction and two suc­
cessive one-electron oxidation processes. Although QBBP shows no
fluorescence and low intersystem crossing (ISC) efficiency, it has
Fig. 5. Cyclic voltammogram of QBBP-OMe measured in THF containing tet­ considerable photothermal conversion efficiency (η = 41%) and desir­
rabutylammonium perchlorate (0.1 M) as a supporting electrolyte. Platinum able as a photothermal-photodynamic therapy agent. Further modifi­
wire was used as the working and counter electrodes. The scan rate was 100 cations of quinoid-bisboron pyrrole with double BF2 chelation and
mV s− 1. Ferrocene is used as an internal standard ((half-wave potential) 0.65 V applications in optical materials and photo-electronic device studies are
vs Ag/AgCl). in progress.

CRediT authorship contribution statement

2.7. In vitro cellular photothermal imaging
Yue Liang: Synthesis, Spectrum measurement, Writing – original
Finally, to visualize the effect of phototherapeutic performance of draft. Dongxiang Zhang: Structure determination, Writing – original
QBBP-H, the cell survival staining was investigated (Fig. S5). After draft. Jie Wang: Cell imaging. Meiheng Lv: MO calculations. Feng Yan:
human colon cancer cells were cultured to a certain density, cells in Investigation. Zhangrun Xu: Writing – review & editing. Jianjun Du:
different dishes were treated with control group, sole light treatment Conceptualization, Writing – review & editing. Xin-Dong Jiang: X-ray
group, sole dye treatment group, and dye treatment followed by light crystallographic analysis, Conceptualization, Writing – review &
irradiation. 690 nm NIR laser (10 mW cm− 2, 20 min) was employed as editing.
the light source, and QBBP-H concentration was 5 μM. Calcein AM
indicated living cells (green fluorescence) and Prodium Iodide PI indi­ Declaration of competing interest
cated dead cells (red fluorescence). By laser confocal microscope im­
aging observation, the initial three groups showed significant green The authors declare that they have no known competing financial
fluorescence (Fig. S5), and almost no red fluorescence was observed. interests or personal relationships that could have appeared to influence
Once light irradiation was undertaken, the red fluorescence was the work reported in this paper.
observed, and almost no green fluorescence remained. Moreover, the
bright field imaging revealed that the cancer cells became round,

5
Fig. 6. a) Time-dependent photodegradation of 6 × 10− M DPBF with 4 μM QBBP-H; b) DPBF degradation rate curves with QBBP-H (S = − 0.0097) in toluene.

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Y. Liang et al. Dyes and Pigments 206 (2022) 110613

Fig. 7. a) Photothermal conversion of QBBP-H at different concentrations (10, 20 and 30 μM) in THF under 690 nm laser irradiation (0.6 W cm− 2). The inner panel
displays photothermal images of QBBP-H in THF under 690 nm laser irradiation (0.6 W cm− 2, 5 min); b) Photothermal conversion of QBBP-H (30 μM) under 690 nm
laser irradiation with different exposure intensity (0.2, 0.4 and 0.6 W cm− 2); c) Photothermal response curves of QBBP-H aqueous solutions (30 μM) under irra­
diation and after naturally cooling to room temperature; d) Linear fitting of − Lnθ and time.

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