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Charge Transfer
Phenothiazine Scope: Steric Strain Induced Planarization and Excimer
Formation
Deng-Gao Chen+, Yi Chen+, Cheng-Ham Wu, Yi-An Chen, Meng-Chi Chen, Jia-An Lin,
Chun-Ying Huang, Jianhua Su, He Tian,* and Pi-Tai Chou*
Abstract: Phenothiazine derivatives based on the 10-phenyl-
10H-phenothiazine (NAS) chromophore, namely 7-phenyl-
7H-benzo[c]phenothiazine (NAS-1) and 12-phenyl-12H-
benzo[a]phenothiazine (NAS-2), were designed and synthe-
sized. NAS-1 and NAS-2 are constitutional isomers with
different steric strains imposed on the phenothiazine core
moiety. In solution, the more-strained NAS-2 possesses a bent
structure and undergoes photoinduced structural planarization
(PISP). In the crystal, despite the absence of PISP, bent NAS-2
exhibits prominent excimer emission as well as emission
mechanochromism, which is not observed in the planar-like
NAS and NAS-1. This unconventional observation results
from the bent core structure facilitating p–p stacking of the
peripheral naphthalene moieties. Two-photon-coupled depth-
dependent emission shows spectral differences between the
surface and kernel of the NAS-2 crystal, and is believed to be
a general phenomenon, at least in part, for materials exhibiting
emission mechanochromism.
Photoinduced structural planarization (PISP) is a fascinating
and promising phenomenon that has received much atten-
tion.[1] Recent examples are focused on the class of molecules
bearing an N,N’-disubstituted-dihydrodibenzo[a,c]phenazine
chromophore (DPAC; see Figure 1 a).[2] Different from the
early reported PISP molecules that reveal an intrinsic non-
planar structure free from steric perturbation,[2] bent DPACs
are purportedly a result of the steric hindrance imposed on
the DPAC moiety, which, upon optical excitation, undergoes
structural planarization resulting in a large Stokes-shifted
emission. By exploiting the resulting structure-dependent
emission properties, diverse applications of PISP molecules
have been reported, including white-light generation,[3]
hydrolysis,[2d] and sensing for self-assembled metallacycles.[2a]
To generalize, as well as extend the scope of PISP
compounds, in this study, a new class of compounds bearing
[*] D.-G. Chen,[+] Y. Chen,[+] C.-H. Wu, Y.-A. Chen, M.-C. Chen, J.-A. Lin,
C.-Y. Huang, Prof. P.-T. Chou
Department of Chemistry, National (Taiwan) University
Taipei, 10617 (Taiwan, R.O.C)
E-mail: chop@ntu.edu.tw
Y. Chen,[+] J. Su, H. Tian
Key Laboratory for Advanced Materials and Institute of Fine
Chemicals, East China University of Science & Technology
Shanghai 200237 (P. R. China)
E-mail: tianhe@ecust.edu.cn
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201906083.
Angew. Chem. Int. Ed. 2019, 58, 13297 –13301 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemie
International Edition: DOI: 10.1002/anie.201906083
German Edition: DOI: 10.1002/ange.201906083
phenothiazine was synthesized, including 10-phenyl-10H-
phenothiazine (NAS), 7-phenyl-7H-benzo[c]phenothiazine
(NAS-1), and 12-phenyl-12H-benzo[a]phenothiazine (NAS-
2; Figure 1 a). NAS-1 and NAS-2 are strategically designed to
act as constitutional isomers, but are subject to different steric
strains in the core chromophore benzophenothiazine. The aim
of this study is twofold. Firstly, we intend to explore if
heterocyclic systems other than DAPC are able to undergo
PISP, broadening its utility in chemistry. Secondly, by access-
ing isomers with distinct steric strain, the mechanism of the
structure–PISP relationship can be explored. Also, pheno-
thiazines are emerging materials which have been recently
reported to show persistently long phosphorescence suitable
for potential applications in bioimaging.[4]
As a result, NAS-2, which possesses a markedly bent
structure, undergoes prominent PISP, generalizing the mech-
anism of PISP governed by steric hindrance. Moreover, in the
solid state, unlike the conventional stacking planar structure
induced excimeric reaction,[5] the bent NAS-2 reveals anom-
alous excimer formation and mechanochromism.[6–7] The
former is rationalized by the bent core structure facilitating
p–p* stacking of the peripheral naphthalene moieties. As for
the latter, comprehensive spatially resolved two-photon
luminescence spectroscopy points to mechanochromism,
which may, in part, originate from different surface-to-
volume ratios, depending on the way the solid is prepared.
Detailed results and discussions are elaborated below.
The syntheses of NAS, NAS-1, and NAS-2 were achieved
using the Buchwald–Hartwig reaction.[7] Details of the
synthetic route are elaborated in the Supporting Information,
and all studied compounds were fully characterized. More-
over, the structures of NAS,[8] NAS-1, and NAS-2 were
confirmed by X-ray analysis as shown in Figure 1 b. Among
them, the bending angle in the phenothiazine core, defined as
the dihedral angle ]C1-N1-S2-C2 (Figure 1 a), which also
represents the bending angle between planes 1 and 2 (Va ;
Figure 1 b), is on the order of NAS (152.0888) > NAS-
1 (147.8988) > NAS-2 (131.1288). For NAS and NAS-1, the
appended N-substituted phenyl rings show a perpendicular
orientation with respect to the phenothiazine chromophore,
while NAS-2 has a structure showing parallel orientation
between the substituted phenyl ring and the core chromo-
phore.[2] For comparison, computational approaches were
also employed by using the density-function theory (DFT)
optimized structures for the titled molecules, and the results
are shown in Figure 3 (NAS-2) and Figure S6 (see the
Supporting Information; NAS and NAS-1). The computa-
tional results are consistent with crystal structure in terms of
trends of Va, which is on the order of NAS (143.5188) > NAS-
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Figure 1. a) Chemical structure of phenothiazine derivatives. b) Single-crystal structures viewed along the N@S axis, together with values for the
bending angle (Va, Vb and Vc) of the phenothiazine skeleton. c) Frontier molecular orbital contours of the titled molecules in optimized excited-
state geometries. Steady-state absorption in toluene solution (black dash line) and photoluminescence spectra (solid line) of d) NAS, e) NAS-1,
f) NAS-2, and g) DPAC in various solvents at room temperature. Note that blue, green, yellow, and red represent cyclohexane, toluene,
dichloromethane and acetonitrile solutions, respectively.

1 (142.9488) > NAS-2 (133.0588), indicating that the bending
structure resolved from the X-ray structure is not mainly
caused by lattice packing. This data leads us to safely conclude
that NAS-2 possesses a bent angle Va between planes 1 and 2
(Figure 1 b), intrinsically resulting from the steric hindrance
introduced by benzo[a]phenothiazine (cf. benzo-
[c]phenothiazine in NAS-1).
The normalized absorption and emission spectra of the
studied phenothiazines are shown in Figures 1 d–f. For
reference, DPAC spectra are depicted in Figure 1 g. NAS
and NAS-1 exhibit an onset of the lowest-lying absorption
band around 430 and 465 nm, respectively. In sharp contrast,
the absorption onset of NAS-2 is in much higher energy of
about 400 nm. Compared to NAS-1, the larger S0-S1 energy
gap for NAS-2 derives from more bent structure, which
restricts the p-electron delocalization. In fact, NAS-2 reveals
a similar absorption spectral profile to that of DPAC,[2]
affirming the bent feature of the benzo[a]phenothiazine
moiety. Further support is rendered by the calculated frontier
orbitals for the titled compounds (Figure 1 c), and NAS and
NAS-1 exhibit a more delocalized type p–p* transition,
whereas it is apparent that the lowest lying transition of NAS-
2 mainly possesses a slight charge-transfer character between
plane 1 (HOMO) to plane 2 (LUMO; Figure 1 b), and higher
calculated vertical transition energy (ca. 375 nm) than that
(ca. 410 nm) of NAS-1 (see Tables S6 and S8). The latter is
also consistent with the experimental results.
Distinct emissive properties are also obtained for the
studied phenothiazines. Among them, both NAS (Figure 1 d)
and NAS-1 (Figure 1 e) show emission that is a mirror image
with respect to the lowest-lying absorption band with 1.04 and
9.03 % quantum yields (Q.Y.), respectively, recorded in
cyclohexane solution. Also, as shown by the purple circles
in Figures 1 d,e, the onset of the emission coincides with that
of the absorption, indicating a normal emission nature.
Although NAS-2 shows similar Q.Y. (8.99 %) in cyclohexane
solution compared with NAS-1, the onsets of absorption and
emission for NAS-2, specified by the blue and red circles
(Figure 1 f,g), are further separated, indicating different
configurations between the originally prepared and structur-
ally relaxed S1 states. The result is essentially the same as the
emissive character of DAPC where the separation between
the onset of absorption (circled in blue) and emission (circled
in red) is obvious (see Figure 1 g). We thus conclude that as
for DAPC, PISP takes place in NAS-2.[2]
To gain in-depth insight into the PSIP of NAS-2,
fluorescence up-conversion techniques were conducted for
NAS-2 in toluene. In this approach a 380 nm (ca. 90 fs) laser
was selected as the excitation pulse, which is near the onset of
the lowest transition. This pulse was chosen to avoid the
higher-lying vibronic relaxation processes that interfere with
the interpretation. The fluorescence decay dynamics were
then monitored at various wavelengths to trace the temporal
evolution. Upon monitoring at 460 nm in the region of the
onset of the emission band (see Figure 1 f), the kinetic trace
consists of a system limited rise (< 120 fs) and a single
exponential decay component. The latter is fitted to be 0.7 ps,
the fast decay of which is attributed to slight structural
relaxation. This data can be supported by monitoring at, for
example, 520 nm, in which the 0.7 ps decay component for
460 nm emission becomes the rise component, accompanied
by a long rise component that still increases its intensity at the

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end of the acquisition window of 30 ps (Figure 2). This long
rise component is further fitted to be 28 ps (Figure S3). Upon
monitoring at longer emission wavelengths, such as 560 nm
and 600 nm, the 0.7 ps rise component gradually disappears
and the 28 ps rising curve becomes the major component (see
Figure 2), followed by a much longer population decay time
that cannot be resolved by the fluorescence up-conversion
study. This population decay is further measured, by a time
correlated single-photon counting (TCSPC) technique, to
have a lifetime of 12.22 ns (see Figure S2 and Table S3).
Figure 2. Femtosecond fluorescence transients (open circles) of NAS-2
in toluene at room temperature observed at the various wavelengths
indicated. The black solid lines denote the instrument response
functions (IRF) and the colored lines represent the fitting curves. The
fitted results are tabulated in Table S3. lex : 380 nm.
The above resulting relaxation dynamics for NAS-2 can
be rationalized by a sequential kinetic pattern expressed as
R* K!t1
I* K!
t2
P* , where R* specifies as the initial optically
prepared excited state, I* denotes the intermediate state, and
P* represents the final planarized states. The first decay time
constant (t1) of 0.7 ps observed at 460 nm is reasonably
assigned to a fast structure relaxation pathway, forming the
intermediate state (I*). This 0.7 ps time constant can also be
recorded from 520 to 600 nm as a rise component becasue
these emission regions mainly originate from I*, which acts as
a successor of R*. The small time constant indicates a small
change of the structure during the R*!I* process. This
change is evidenced by the calculated structures of R* and I*
shown in Figure 3, and they reveal a rather small difference in
Va and Vb between R* and I*. Then, a subsequent I*!P*
process takes place, for which the time constant t2 is as long as
28 ps, resolved from the rise component of the P* monitored
at 600 nm. The long t2 clearly indicates that the I*!P*
process involves a large-amplitude motion, and is also
supported by the significant difference in Va between I* and
P* (Figure 3). In comparison, the planarization time constant
of 28 ps (i.e. the formation of the P* state) for NAS-2 as
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Figure 3. DFT-optimized structures of NAS-2 with recorded values for
the bending angle in phenothiazine chromophore (Va) and the two
bending angles (Vb and Vc) in the six-membered ring in the R*, I*,
and P* states, respectively.
observed from 520 to 600 nm is significantly longer than that
(cf. 7.8 ps) of DPAC.[1b] The result may result from the
chemical difference between the core moieties phenothiazine
(NAS-2) and phenazine (DPAC) where sulfur and nitrogen,
respectively, play a key role in the planarization. The lone-
pair electrons on the sulfur atom in phenothiazine is less
susceptible to the p-conjugation than that of nitrogen center
in phenazine, providing less of a driving force for PISP in
NAS-2.
Further support of the structure–PISP relationship is
provided by computational approaches in which NAS-2 was
fully optimized in the ground state to exhibit a global energy
minimum R state and hence its lowest-lying excited state R*
by vertical, that is, Franck Condon excitation. I* and P* states
were obtained by the fully optimized S1 state to achieve its
local and global energy minimums. As shown in Figure 3, the
computational results indicate that the bending angle (Va)
changes from 133.05 to 130.2788 in the I* state with a more bent
V-shaped geometry. This structure can be considered as
a local energy minimum, from which the transformation starts
to take place, resulting in the nearly planarized (Va = 173.8788)
global minimum geometry in the P* state. Additionally, the
other two bending angles in the middle six-membered ring of
the phenothiazine, denoted Vb and Vc, are extended from
113.7888 and 97.9988 to 123.7188 and 103.0788 in R* and P* states,
respectively (see Figure 3). The expansion of the two bending
angles in the six-membered ring (i.e. Vb and Vc) indicates
more delocalization of the p-electrons in the phenothiazine
skeleton, driven by the energy stabilization to gain aroma-
ticity. The net result is to reduce the p–p* energy gap. The
calculated S1!S0 of 584 nm for P* (see Tables S8–S10)
matches well to the experimentally observed emission at
about 550 (Figure 1 f). In stark contrast, the result of the
calculations assess a small change of Va for NAS and NAS-
1 after structural relaxation in the S1 state (see Figure S4),
supporting their normal emission behavior.
In the crystal, the imposed lattice energy forbids PISP,
therefore, one expects NAS-2 to exhibit normal Stokes-
shifted emission, similar to that of NAS and NAS-1 [see
Figure S1(a) and S1(b)]. Unexpectedly, NAS-2 exhibits dual
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Figure 4. a) The emission spectra of the area in the merged imagins shown within the red square in (d) as recorded from surface to kernel (color
solid line) combined with the photoluminescence spectra of NAS-2 in powdered solid (black solid line). Inset: Observation by the naked eye of
the crystal and powdered solid form of NAS-2 under 365 nm UV lamp irradiation. b) NAS-2 and c) NAS-1 with recorded values for distance
between two proximal congeners. e) The transient photoluminescence characteristics of NAS-2 in the crystal as monitored at various wavelengths.
Note that lex = 760 nm was employed for two-photon studies, lex = 380 nm for transient measurements, and lex = 350 nm for PL measurement.
Black dashed line in (a) denotes that the emission spectra by two-photon studies started from 420 nm due to the instrument limitation, and the
IRF in (e) represents the instrumental response function. The results were all recorded at room temperature.

emission, maximized at 390 nm and 520 nm and denoted as F1
and F2 bands, respectively, in the crystal (Figure 4 a). In
comparison, DPAC also shows a normal 386 nm emission
band in the crystal [see Figure S1(d)]. Therefore, the assign-
ment of the F1 band to the normal emission of the bent
structure is unambiguous. It is reasonable to conclude that the
F2 band observed in the crystal originates from emission
induced by the intermolecular interactions, most plausibly the
excimer-like emission. This viewpoint is supported by the
difference in the molecular packing in the crystal between
NAS-2 and NAS-1 (Figures 4 b and c), where NAS-2 shows
a p–p stacking between adjacent benzo[a]naphthalene moi-
eties with a decent distance of 3.34 c (recorded from C8 to
C9’ and C9 to C8’ as shown in Figure 4 b) for the intermo-
lecular interaction. Figure 4 b clearly shows that the bent
phenothiazine in NAS-2 avoids the steric hindrance between
the N-phenyl (molecule 1) and the adjacent phenothiazine
(molecule 2) moieties, affording a proximal p–p interaction
for the benzo[a]naphthalene moieties. On the contrary, as
shown in Figure 4 c, the more-planar NAS-1 has different
molecular packing where the benzo[c]naphthalene moieties
are arranged in opposing directions between adjacent NAS-
1 molecules, avoiding any possible p–p stacking interactions.
Of equal importance is the observation of the so-called
mechanochromism for NAS-2 in the solid state, where the
emission color, observed by the naked eye, changes from pale
blue in the crystal to deep blue upon grinding the crystal
(Figure 4 a).[5] We then employed two-photon excitation
microscopic fluorescence imaging to investigate the NAS-2
crystal as a function of the depth of crystal from its surface.
Upon two-photon (380 nm) excitation and probing the sur-
face of the crystal, NAS-2 exhibits mainly a 390 nm emission
band, appearing as the purple-blue emission hue (Figure 4 d;
the probing region is specified by the area within the red
square). Upon increasing the depth of the excitation, the
apparent 500 nm excimer emission increases (Figure 4 a),
reaching a maximum at about 14 mm, which is nearly at the
kernel of the prepared crystal. In comparison, the emission of
the powdered NAS-2 solid (Figure 4 a) is dominated by
a 390 nm emission (see black solid line). Moreover, the
transient photoluminescence of the NAS-2 crystal (Figure 4 e)
also supports the observations. By monitoring at a normal
emission of 400 nm, the up-converted signal shows a fast
decay component of 20.8 ps, accompanied by a long popula-
tion decay time of 1.0 ns, which is further resolved by TCSPC
[see Figure S4(a) and (b)]. The 20.8 ps matches well with the
rise component of 21.3 ps monitored at the excimer emission
of 500 nm (Figure 4 e). Also, a population lifetime the excimer
emission is measured to be 1.5 ns [see Figure S4(b) and (b)].
Accordingly, it is reasonable to assign the 1.0 ns decay
component for the 400 nm emission to the decay of normal
emission on the crystal surface where excimer formation is
prohibited.
Having gathered the above observations, we are thus able
to assert the formation of the excimer in the kernel versus the
interruption of the excimer formation on the surface because
of the rupture of the ordered stacking by the dangling NAS-2
molecules. The observation of mechanochromism upon
grinding in this study is attributed to the increase of surface-
to-volume ratio that suppresses the excimer formation.[5]
Note that the continuous growth of the excimer emission
from surface to kernel shown in Figure 4 e is due to the

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resolution in depth, which is limited to about 1 mm in this
study.
In summary, a series of phenothiazine derivatives were
synthesized and characterized. For NAS-2, it is observed that
the replacement of one N-phenyl functionality in DPAC with
sulfur atom leads the molecule to undergo PISP, and hence
a large Stokes-shifted emission. In comparison to the NAS-
1 isomer, the steric hindrance imposed by the benzo-
[a]naphthalene moiety plays a key role in the bent NAS-2
structure, and is also the origin of the PISP. The result
generalizes the PISP mechanism for benzophenazines and
benzophenothiazines and is believed to be applicable to other
heterocyclic congeners. In the crystal, despite the prohibition
of PISP, bent NAS-2 exhibits prominent excimer emission
that is not observed in the planar-like structures of NAS and
NAS-1. This unconventional observation is rationalized by
the bent core structure facilitating p–p stacking of the
peripheral naphthalene moieties. Finally, the depth-depen-
dent ratiometric intensity for normal versus excimer emission
in the crystal leads us to conclude that the emission
mechanochromism for NAS-2 mainly originates from the
difference in the surface-to-volume ratio between the crystal
and its powder form. This observation is believed to be
a general phenomenon, or at least in part, for other materials
claimed to exhibit emission mechanochromism. Using phe-
nothiazines as a prototype we thus established the relation-
ship among structures, PISP properties, excimeric reactions,
and mechanchromism.
Supporting Information. The Supporting Information is
available free of charge via the Internet. Synthetic methods
for the compounds, NMR, and computational details are
provided.
Crystallographic data. CCDC 1878210 (NAS-1), 1878211
(NAS-2) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre. Notes that
NAS CCDC number is 1135756, which is reported in previous
research.[7]
Acknowledgements
P.-T.C. thanks the Ministry of Science and Technology
(MOST), featured areas research program within the frame-
work of the Higher Education Sprout Project administrated
by Ministry of Education (MOE) of Taiwan, for financial
support. H.T. thanks NSFC/China (21788102) for financial
support. We are grateful to the National Center for the
valuable computer time and facilities at the High-perfor-
mance Computing (NCHC) of Taiwan for.
Conflict of interest
The authors declare no conflict of interest.
Keywords: charge transfer · conformation analysis · excimers ·
heterocycles · steric hindrance
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Manuscript received: May 15, 2019
Revised manuscript received: July 19, 2019
Accepted manuscript online: July 23, 2019
Version of record online: August 13, 2019
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