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org/JPCC Article

Achieving Different Color Changes for Photochromic Compounds by

Controlling Coordination Modes
Yong-Fang Han, Ning-Ning Zhang, Ming-Sheng Wang,* and Guo-Cong Guo*
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ABSTRACT: Photochromic materials with different color changes are

highly desirable for color indicators, anticounterfeiting marks, decoration, and
Downloaded via UNIV OF NEW ENGLAND on December 7, 2020 at 14:47:07 (UTC).

other applications. Group modification and coordination with metals are

common methods to obtain such materials. This work demonstrates that
different coordination modes can acquire different color changes. Two known
compounds, [Zn(suc)(bipy)]n (1) and [Zn2(mal)2(μ-bipy)(H2O)2·2-
(H2O)0.25]n (2) (suc = succinate, mal = malonate, bipy = 4,4′-bipyridine),
exhibit different photochromic behaviors: compound 2 with dicoordinated
bipy groups shows significant red-shift absorption compared to 1 with
monocoordinated bipy groups after illumination. This discovery provides a
new idea to develop photochromic materials with tailored color changes.

■ INTRODUCTION
Photochromism refers to the reversible transformation of a
chemical species between two forms, with different absorption
spectra, induced in one or both directions by the absorption of
electromagnetic radiation.1 For color-related applications of
photochromic compounds, such as color indicators,2,3
anticounterfeiting marks,4−7 decoration,8 sunglasses,9 and
other applications,10−16 different color changes are highly
desirable. Group modification and coordination with metals
have been demonstrated as two successful methods to achieve
different color changes. For instance, the Irie group obtained
different colored diarylethlenes by introducing different groups
at specific sites and demonstrated potential applications in full-
color displays or multifrequency 3D optical storage media;17,18
Yam and co-workers revealed that modifying diarylethenes by
metal coordination could result in near-infrared (NIR)
absorption, which is especially important for optical memory
storage.19−21 Variation of electronic structures for photo-
chromophores is the main reason for different color changes
when adopting the two abovementioned methods. As for the
coordination method, different coordination modes of one
photochromophore must bring different electronic structures
and thus may generate multiple color changes. However, there
were no previous examples to demonstrate this possibility.
Viologen compounds and analogues are a kind of typical
photochromic compound. Upon irradiation, viologen cations
and analogues, with an excellent electron-deficient nature, can
undergo a redox process and generate different states with the
assistance of electron-rich species. As shown in Figure 1,
theoretical electron absorption bands (calculated at the
B3LYP/def2tzvp level by the TD-DFT method) for one-
electron-reduced mono- or disubstituted 4,4′-bipyridinium by
the CH3+/H+ group are significantly different. Absorption
bands in the visible region for disubstituted radical species
show a clear red shift compared with those for monosub-
stituted radical species, giving a difference of nearly 100 nm.
Because metal ions are also cations, it is predicable that
different colors can be achieved through replacing the CH3+/
H+ cations with metal ions and changing coordinated modes.
In our previous work, we have found that coordination
assembly of some nonionic N-heterocyclic aromatic ligands
with the other ligands bearing nonbonding lone pairs of
electrons is an effective approach to obtain the so-called
metalloviologen compounds showing electron-transfer photo-
chromic behavior.22,23 Metalloviologen compounds have the
following three advantages: (1) the ligand precursors do not
need to be alkylated first as is the case for traditional viologen
compounds, which avoids complicated synthetic steps and
sometimes the use of toxic halogenated reagents; (2) the
system is easier to expand because of the availability of a great
variety of nonionic N-heterocyclic aromatic ligands, either
monocyclic or polycyclic, and many metals with diverse
coordination modes; (3) many metal centers have fascinating
optical, electrical, and magnetic properties, which may result in
richer system properties. A series of metalloviologen
compounds built with bipyridyl ligands, such as 4,4′-bipyridine
(bipy), have been explored by our and other groups.24−33
Bipyridyl ligands have mono- and dicoordinated modes and
Received: September 29, 2020
Revised: November 23, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jpcc.0c08857

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Figure 1. Electronic absorption spectra obtained by TD-DFT calculations at the B3LYP/def2tzvp level for one-electron-reduced PQ+/MQ+ (N-
proton-4,4′-bipyridinium/N-methyl-4,4′-bipyridinium) and PV2+/MV2+ (N,N′-diproton-4,4′-bipyridinium/N,N′-dimethyl-4,4′-bipyridinium).
Interannular torsional angles (δ) of all calculation models were set to zero.
thus are ideal models to investigate the relationship between
coordination and color changes.
In this work, two known compounds, [Zn(suc)(bipy)]n (1,
CCDC no. 162192; suc = succinate, bipy = 4,4′-bipyridine)
and [Zn2(mal)2(μ-bipy)(H2O)2·2(H2O)0.25]n (2, CCDC no.
607468; mal = malonate), are selected as the research
models.34,35 The bipy ligands with nearly plane structures are
monocoordinated in 1 and dicoordinated in 2. The same type
and coordination mode of the Zn atoms minimize the impact
of the coordination environment. Both the compounds show
typical electron-transfer photochromic phenomena: light
triggers electron transfer with the generation of stable radical
products, and the products undergo back electron transfer after
thermal annealing. The biggest difference is that absorption
bands of the radical product for 2 are clearly red-shifted
compared with those for 1. Structural analysis and theoretical
calculations revealed that this difference is primarily caused by
the different coordination modes.
■
EXPERIMENTAL SECTION
Materials and Physical Measurements. All chemical
reagents and solvents used in the synthesis experiments were in
analytical grade without further purification. Powder X-ray
diffraction (PXRD) patterns were recorded on a Rigaku
MiniFlex 600 diffractometer using Cu Kα radiation (λ =
1.5406 Å). Simulated PXRD patterns were produced by the
free Mercury Version 3.10.2 software using the X-ray single
crystal diffraction data. Elemental analyses were done on the
Elementar Vario EL III microanalyzer. FT-IR spectra were
measured at room temperature in the 4000−400 cm−1 range
on a PerkinElmer Spectrum One Spectrometer using KBr
pellets as one reference. Electronic absorption spectra were
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achieved in the diffuse reflectance mode on a PerkinElmer
Lambda 950 UV/Vis/NIR spectrophotometer equipped with
an integrating sphere attachment and BaSO4 as the reference.
Electron spin resonance (ESR) spectra were collected on a
Bruker ER-420 spectrometer with a 100 kHz magnetic field in
the X band. Thermal stabilities were tested through a TGA/
DSC Mettler Toledo thermal analyzer under the atmosphere of
N2 with a heating rate of 5 K·min−1. A Newport Co. Pulseo
GKNQL-355-3-30 diode-pumped solid-state (DPSS) laser
(355 nm; 70 kHz; 39 ns pulse width; ca. 1.55 mJ cm−2; spot
size, ca. 1.5 cm) was used as the light source to irradiate
samples for various tests. In order to ensure more accurate and
scientific experimental data, all tests relating the initial and
colored states were done using the same sample.
Computational Approaches. 1. Calculations of electronic
absorption spectra. The electronic absorption spectra for
optimized structural models of one-electron-reduced PQ+/
MQ+ (N-proton-4,4′-bipyridinium/N-methyl-4,4′-bipyridi-
nium) and PV2+/MV2+ (N,N′-diproton-4,4′-bipyridinium/
N,N′-dimethyl-4,4′-bipyridinium) were calculated by the
Gaussian 09 program with the B3LYP functional and the
def2tzvp basis set.36,37 Ground-state geometries of these
models were optimized at the M06-2X/def2tzvp level and
the interannular torsional angles (δ) were set to zero, agreeing
with the nearly plane structures of bipy ligands in 1 and 2 as
much as possible. The calculation results were analyzed by
Multiwfn.38
2. Calculations of total and partial density of states (TDOS/
PDOS). DOS for all compounds was calculated using the
CASTEP package.39 The structural models were built directly
from the single-crystal X-ray diffraction data. The exchange−
correlation energy was described by the PBE functional within
the GGA.40,41 The norm-conserving pseudopotentials were
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chosen to modulate the electron−ion interaction. The plane-
wave cut off energy was 750 eV, and the threshold of 1 × 10−6
eV was set for the self-consistent field convergence of the total
electronic energy. Other parameters were set to default values.
Calculated results are corrected with scissor operators based on
measured optical gaps.
Synthesis. All compounds were prepared via modified
literature procedures.34,35 As for 1, a mixture of Zn(NO3)2·
6H2O (0.149 g, 0.50 mmol), succinic acid (0.059 g, 0.50
mmol), bipy (0.078 g, 0.50 mmol), NaOH (0.040 g, 1 mmol),
and H2O (6 mL) was sealed in a 23 mL Teflon-lined autoclave
and heated at 100 °C for 3 days. For 2, ZnO (0.081 g, 1.00
mmol), malonic acid (0.208 g, 2.00 mmol), and bipy (0.047 g,
0.30 mmol) were dissolved in a mixture of N,N-dimethyfor-
mamide (DMF) (1 mL) and H2O (4 mL) and placed into a 23
mL Teflon-lined autoclave before heating at 65 °C for 3 days.
The yielded naturally cooled solution was filtered and then
washed by 10 mL ethanol or ether to obtain nearly colorless
crystals. All crystal samples used for tests were manually picked
and separated with the assistance of a microscope, and their
phase purity was verified by PXRD, IR (Figures S1 and S2),
and elemental analyses of C, H, and N. Anal. calcd for 1: C,
58.37; H, 4.08; N, 11.34. Found: C, 58.41; H, 4.00; N, 11.16%.
Anal. calcd for 2: C, 35.88; H, 3.11; N, 5.23. Found: C, 35.21;
H, 3.14; N, 5.00%.
It is to be noted that all the freshly obtained samples should
be treated in dark because of their sensitivity to sunlight.
■
RESULTS AND DISCUSSION
Crystal Structure. Crystal structures of 1 and 2 have been
fully characterized by other groups, so they are delineated
briefly.34,35 Both compounds have one- and three-dimensional
structures, respectively, in which all Zn2+ ions adopt the six-
coordinated mode. As shown in Figure 2, the bipy ligands are
Figure 2. Coordination structures for 1 and 2. δ represents
interannular torsional angles of the bipy group. One thermally
disordered part of the bipy ligand in 2 is shown. H atoms are omitted
for clarity.
monocoordinated in 1 and dicoordinated in 2, and their
interannular torsional angles are approximately 4.35 and 0.00°,
respectively. There was thermal disorder in the bipy parts of 2,
but it did not affect the subsequent analysis results.
Photochromism. Compounds 1 and 2 exhibit photo-
chromic behaviors in the solid state under ambient conditions.
The as-synthesized crystalline sample of 1 appeared to be light
yellow, but turned dark yellow after illumination by a DPSS
laser under the atmosphere conditions and reached absorption
saturation within 30 min (Figure 3c). Correspondingly,
electron absorption spectra exhibited a slight enhancement at
284 nm and a new electronic absorption band covering the
350−500 nm region (Figure 3a). The broad band peaks at 401
nm, as shown in the differential electron absorption spectrum
(Figure 3b). Upon continuous irradiation with a DPSS laser in
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air at room temperature, the as-prepared colorless sample of 2
turned green and reached saturation after 20 min (Figure 3f).
Meanwhile, the electronic absorption intensity increased at 279
nm, and two new obvious electron absorption bands emerged
at ∼406 and 645 nm (Figure 3d,e).
To make sure electron transition occurs upon irradiation,
DOS and partial DOS (PDOS) calculations using the CASTEP
package based on the single-crystal X-ray diffraction data of 1
and 2 were performed. Because the calculated results were
corrected with scissors operators (1.23 eV for 1 and 0.72 eV
for 2), which were obtained by subtracting the calculation
results (Figure S4c,d) from the optical band gaps (Figure
S4a,b), photoinduced electron transitions can be judged from
the contribution of each component. The electron absorption
bands around 280 nm for unirradiated samples of 1 and 2
(Figure 3) correspond to the electron transition between the
valence band maxima Γa and the conduction band minima Γb
(Figure 4). The valence band maxima Γa of 1 and 2 were
mainly dominated by bonding p-orbitals of the carboxyl
groups, and the conduction band minima Γb were contributed
by the bipy groups (Figures 4 and S5). Therefore, photo-
induced electron transitions of 1 and 2 happened from the
carboxyl groups to the bipy groups.
As depicted in Figure 5, both 1 and 2 were ESR-silent before
irradiation but displayed clear signals around 2.0033 (g =
2.0046 and linewidth = 16 Gauss for 1 and g = 2.0046 and
linewidth = 13 Gauss for 2). The appearance of a sharp ESR
signal close to that of a free electron indicates the generation of
radical species. PXRD patterns and IR spectra of 1 and 2 did
not show significant changes in the coloring and fading
processes, which indicates that no other side reactions
occurred, such as photoinduced isomerization or photolysis
(Figures S1 and S2). Therefore, the photoinduced coloration
of 1 and 2 should originate from inter-/intramolecular
photoinduced electron transfer. The increased electron
absorption around 240 nm for the irradiated samples of 1
and 2 (Figure 3) can be assigned to the presence of carboxylate
radicals according to the literature.42 The two electron
absorption bands for the irradiated sample of 2 agree well
with those for viologen radicals,43−45 which suggests the
generation of a bipy radical. The potential electron donor in 1
is only the carboxylate group, and so the broad electron
absorption band peaked at 401 for the irradiated sample of 1
(Figure 3) is ascribed to the presence of a monocoordinated
bipy radical. The ESR signals for irradiated samples of 1 and 2
decayed slightly when kept in dark in air but quickly upon
thermal annealing in air. As for the irradiated sample of 1, the
ESR signal almost disappeared after annealing at 180 °C for 6
h (Figure 5a). For the irradiated sample of 2, the ESR signal
weakened slightly when kept in dark in air for 53 days and
more after thermal annealing at 80 °C in air for 4 h (Figure
5b). Continuous annealing at 80 °C in air could not eliminate
the signal completely. Thermal stability data of 2, obtained
from literature reports and experimental re-verification (Figure
S3), indicate that temperatures above 80 °C easily cause
structural collapse. Hence, there is no way to continue studying
the fading conditions through heat up because of the poor
thermal stability of 2, which indicates that it has experienced
quasi-reversible photochromic cycles under this condition.
To further monitor possible electron transfer paths in the
crystal structure of 1 and 2, intermolecular interactions are
investigated. As shown in Figure 6, there are diverse and
complex hydrogen bonds in 1 and 2. They include C10−
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Figure 3. For 1 (a−c) and 2 (d−f), light-induced changes of electronic absorption spectra, differential electronic absorption spectra, and colors in
the solid state under ambient conditions.
Figure 4. Total and partial density of states for 1 (a) and 2 (b).
Figure 5. ESR spectra for 0.5 mmol crystalline samples of 1 (a) and 2
(b): (black) as-synthesized, (orange) illuminated by the DPSS laser
under ambient conditions, (purple) decolored in dark, and (green)
decolored by thermal annealing.
Figure 6. Hydrogen bonds (green dashed lines; green represents the
H atom) in the crystal structures of 1 (a) and 2 (b). The blue parts
represent the electron acceptors and the red parts are the electron
donors. The partial green arrows indicate the directions of electron
transfer.
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Hbipy···O1suc, C7−Hbipy···O2suc, and C2−Hbipy···O2suc for 1 and
C5−Hbipy···O4mal, C5−Hbipy···O1mal, C4−Hbipy···O2mal, and
C1−Hbipy···O5mal for 2. These hydrogen bonds offer the
possible electron transfer paths from carboxyl groups to bipy
groups. According to the Marcus theory, the shorter the
distance between the donor and the acceptor, the faster the
electron transfer rate will be. Therefore, in the paths
mentioned above, C10−Hbipy···O1suc with the C···O distance
of 3.324(5) Å for 1 and C1−Hbipy···O5mal with the C···O
distance of 2.948(6) Å for 2 should be the most favorable path
for electron transfer.
Photochromic Differences. As mentioned above, com-
pounds 1 and 2 have a significant difference in color change,
although they have the same electron acceptor/donor and
metal center. Structural factors for this difference include the
coordination environment of the Zn atom, geometry of bipy,
interactions around bipy, and coordination mode of bipy.
Influences of these factors are discussed below.
1. Coordination environment of the Zn atom. In 1 and 2, the
coordination geometry of Zn atoms is similar, but the
coordinating atoms, especially the number of N or O atoms,
have a little difference. Some previous examples have found
that, for isostructural compounds with the same photo-
chromophore, different second ligands around one metal
center can lead to different color changes, owing to different
yields of photoproducts, but do not influence positions of
absorption bands. For instance, Lv et al. found that
photoproducts for isostructural MQ+-based halozinc com-
plexes [(MQ)ZnX3] (X = halogen atoms) showed bluish green
and pale green when X is Cl and Br, respectively, but their
absorption bands were all peaked around 610 nm.46 The same
case was observed by Li et al. in isostructural compounds
[ZnX2CEbpy] (X = Cl and Br).47 These examples illustrate
that the coordination environment of the Zn atom is not the
main reason for the difference in color change between 1 and
2.
2. Geometrical configuration of bipy. Bipy ligands in the
crystal structures of 1 and 2 have good planarity, and their
interannular torsional angles are 4.35 and 0.00°, respectively
(Figure 2). To research the influence of different interannular
torsional angles on the electronic absorption spectra, TD-DFT
calculations on the one-electron-reduced bipy group with
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
interannular torsional angles of 4.35 and 0.00° were conducted.
In these calculation models, coordinated atoms are not
included to decrease maximally the influence of coordination.
Calculated electron absorption peaks in the visible region are
529 and 527 nm, respectively, for interannular torsional angles
of 4.35 and 0.00° (Figure S6). It is clear that the interannular
torsional angle has a little effect on the absorption spectra.
3. Interactions around bipy. As depicted in Figure 6, there
are hydrogen bonds in the crystal structures of 1 and 2. These
hydrogen bonds have long separations between the proton
donor and proton acceptor and are thus rather weak. This
means that the influence of hydrogen bonds can be ignored. As
for π stacking interactions between two adjacent bipy groups,
the extent of overlapping and separations between centroids of
pyridyl groups are important indicators. As shown in Figures
S7a,b, there are the set-off shaped or T-shaped π-stacking
interactions between two adjacent bipy ligands in 1 and 2 by
the structural analyses and theoretical calculations with the
B3LYP functional and the def2tzvp basis set, which the
overlapping extents between adjacent bipy ligands in 1 and 2
are very small. In addition, the centroid-to-centroid separations
between adjacent bipy ligands in 1 and 2 are 8.039(4) and
4.958(8) Å, respectively (Figures S7c,d). They are clearly
bigger than 4.5 Å, which is indicative of rather weak π-stacking
interactions. Therefore, interactions around bipy have little
influence on the difference in color change for 1 and 2.
Through the exclusive method, we can draw a conclusion
that the difference in color change between 1 and 2 is primarily
caused by the different coordination modes of the bipy ligand.
■
CONCLUSIONS
In summary, to obtain different color changes for photo-
chromic compounds, group modification and coordination
with metals are common methods to achieve this goal. In this
work, it is demonstrated for the first time that different
coordination modes can lead to controllable color changes.
Two compounds exhibit different photochromic behaviors:
compounds with dicoordinated bipy groups show significant
red-shift absorption compared to the compound with
monocoordinated bipy groups after illumination. Thus, this
method provides a new way to obtain the expected color
changes by regulating the coordination modes of bipy groups
for photochromic compounds.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c08857.
Additional information regarding the PXRD patterns, IR
spectra, TG curve, optical gaps and theoretical band
gaps, total and partial density of states, and calculated
electronic absorption spectra of bipy group with
different interannular torsional angles and interactions
around bipy for 1 and 2 (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Ming-Sheng Wang − State Key Laboratory of Structural
Chemistry, Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences, Fuzhou, Fujian
350002, P. R. China; orcid.org/0000-0002-2400-719X;
Email: mswang@fjirsm.ac.cn
E https://dx.doi.org/10.1021/acs.jpcc.0c08857
pubs.acs.org/JPCC Article
Guo-Cong Guo − State Key Laboratory of Structural
Chemistry, Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences, Fuzhou, Fujian
350002, P. R. China; orcid.org/0000-0002-7450-9702;
Email: gcguo@fjirsm.ac.cn
Authors
Yong-Fang Han − State Key Laboratory of Structural
Chemistry, Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences, Fuzhou, Fujian
350002, P. R. China; University of Chinese Academy of
Sciences, Beijing 100049, P. R. China
Ning-Ning Zhang − School of Chemistry and Chemical
Engineering, Liaocheng University, Liaocheng 252059, P. R.
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c08857
Author Contributions
All authors have given approval to the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (91545201, 21827813, and 22073102),
the Strategic Priority Research Program of Chinese Academy
of Sciences (XDB20010100 and YJKYYQ20180006), Key
Research Program of Frontier Science, and Chinese Academy
of Sciences (QYZDB-SSW-SLH020).
■
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