Self-assembly of emissive metallocycles with tetraphenylethylene, BODIPY and terpyridine in one system

Article abstract of DOI:10.1080/10610278.2019.1659266

Tetraphenylethylene (TPE) related (supra)molecules have been intensively investigated due to their aggregation-induced emission (AIE) effect based on the restriction of intramolecular rotation (RIR). Meanwhile, boron-dipyrromethene (BODIPY) tends to emit intense fluorescence with high quantum yields. Herein, we combined TPE, BODIPY and terpyridine (TPY) into one system to study the emissive behaviour of organic building block as well as a self-assembled metallo-supramolecule. The TPY and BODIPY substituents with bulky sizes provide strong hindrance to restrict the rotation of the phenyl groups on TPE, leading to enhancement of emissive properties in both solution and aggregation states. Furthermore, the BODIPY-TPE-TPY ligand (L) was assembled with Zn (II) through coordination-driven self-assembly to form a cyclic dimer (D) with typical AIE characteristics.

Full text of DOI:10.1080/10610278.2019.1659266

Supramolecular Chemistry
ISSN: 1061-0278 (Print) 1029-0478 (Online) Journal homepage: https://www.tandfonline.com/loi/gsch20
Self-assembly of emissive metallocycles with
tetraphenylethylene, BODIPY and terpyridine in
one system
Yu Yan, Guang-Qiang Yin, Sandra Khalife, Zhan-Hang He, Chen Xu &
Xiaopeng Li
To cite this article: Yu Yan, Guang-Qiang Yin, Sandra Khalife, Zhan-Hang He, Chen Xu &
Xiaopeng Li (2019): Self-assembly of emissive metallocycles with tetraphenylethylene, BODIPY
and terpyridine in one system, Supramolecular Chemistry, DOI: 10.1080/10610278.2019.1659266
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SUPRAMOLECULAR CHEMISTRY
https://doi.org/10.1080/10610278.2019.1659266
ARTICLE
Self-assembly of emissive metallocycles with tetraphenylethylene, BODIPY and
terpyridine in one system
a,b
b
b
a
b,c
b
Yu Yan , Guang-Qiang Yin , Sandra Khalife , Zhan-Hang He , Chen Xu and Xiaopeng Li
a
b
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, China; Department of Chemistry, University of South
c
Florida, Tampa, FL, USA; School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang,
Jiangsu, China
ABSTRACT
ARTICLE HISTORY
Tetraphenylethylene (TPE) related (supra)molecules have been intensively investigated due to their
aggregation-induced emission (AIE) effect based on the restriction of intramolecular rotation (RIR).
Meanwhile, boron-dipyrromethene (BODIPY) tends to emit intense fluorescence with high quantum
yields. Herein, we combined TPE, BODIPY and terpyridine (TPY) into one system to study the emissive
behaviour of organic building block as well as a self-assembled metallo-supramolecule. The TPY and
BODIPY substituents with bulky sizes provide strong hindrance to restrict the rotation of the phenyl
groups on TPE, leading to enhancement of emissive properties in both solution and aggregation
states. Furthermore, the BODIPY-TPE-TPY ligand (L) was assembled with Zn (II) through coordination-
driven self-assembly to form a cyclic dimer (D) with typical AIE characteristics.
Received 20 February 2019
Accepted 18 August 2019
KEYWORDS
Tetraphenylethylene;
aggregation-induced
emission; terpyridine
Introduction
aggregation-induced emission (AIE) characteristic have
attracted considerable attention since 2001 (7). After that,
a broad array of molecular compounds was reported with
no emission or a weak emission in solution but strong
emission under aggregate state (8–11). In the pursuit of
more tunable emissive properties, metallo-supramolecules
with promising AIE characteristic were of great interest
recently through introducing additional restriction of intra-
molecular rotation (RIR) by metal coordination (1, 12).
Among the well-documented fluorophores with AIE
features, tetraphenylethene (TPE) and its derivatives
Metal-organic luminescent materials display tunable opti-
cal properties in sensing and imaging applications (1–4).
Typically, luminescence efficiency of most (supra)molecular
dyes is drastically reduced with increasing concentration.
Such behaviour is generally attributed to the aggregation-
caused quenching (ACQ) effect (5), which would be unde-
sirable in many practical applications (6). For instance,
aggregation between (supra)molecules is inevitable when
fluorescent materials are prepared in solid states or thin
films. In contrast to ACQ, fluorescent materials with
CONTACT Xiaopeng Li
xiaopengli1@usf.edu
Department of Chemistry, University of South Florida, Tampa, FL 33620, USA; Zhan-Hang He
hezhanhang@zzu.edu.cn
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China
©
2019 Informa UK Limited, trading as Taylor & Francis Group

2
Y. YAN ET AL.
that bear a double bond-conjugated centre and rotata-
ble aromatic substituents were introduced in various
systems, ranging from small molecules to polymers,
and from supramolecules to metal-organic (13, 14)
and covalent-organic frameworks (15, 16). Moreover,
the emissive behaviours can be tailored by introducing
additional RIR and/or decorating with fluorophores pos-
sessing high quantum yields (17, 18). In the field of
metallo-supramolecular chemistry, Stang and Yang con-
structed a variety of metallocycles and metallocages
based on RIR through the coordination of Pt(II) compo-
nents with TPE building blocks (19–24). In most of these
reports, the fluorophores within the metallo-
supramolecules were limited to TPE alone. Multiple
types of fluorophores, however, were rarely combined
into one system to tune the emissive properties.
was obtained by purification on Al O and size exclusion
2 3
columns successively with 42% yield.
Efficient self-assembly was performed by adding
a methanol solution of Zn(NO ) ·6H O into a chloroform
3
2
2
solution of L at a 1:1 ratio (Scheme 2). After stirring at 50 ºC
for 3 h, the mixture was cooled to roomtemperature. A red
precipitate of metallocyclic dimer (D) was obtained via
adding excess amounts of NH PF salt. After washing
4
6
with deionised water and methanol, D (yield 90%) was
directly subjected for detailed characterisation without
further purification. Both ligand and assemblies were
1
13
fully characterised by H, C, 2D correlation spectroscopy
(2D-COSY) nuclear magnetic resonance (NMR), and elec-
trospray ionisation time-of-flight mass spectrometry (ESI-
TOF-MS) as well as travelling wave ion mobility-mass
spectrometry (TWIM-MS) (32–34). Furthermore, the optical
properties (UV-visible and fluorescence spectroscopy) of
L and D were studied in good solvent with different frac-
tion of poor solvent contents. Transmission electron
microscopy (TEM) and dynamic light scattering (DLS)
were employed to investigate the aggregation behaviours
of D in different CH CN/methanol as well as CH CN/water
In this work, we combined multiple fluorophores, i.e.
boron-dipyrromethene (BODIPY), TPE and terpyridine
(TPY) into one supramolecular system to study the
emissive behaviour and how these fluorophores contri-
bute to the emission performance. As small chromo-
phores with strong UV-absorbance, BODIPYs could
produce sharp fluorescence peaks with high luminous
efficiency and stability in harsh environments (25, 26).
Thus, we expected to build a supramolecular system
with high luminescent efficiency in both solution and
aggregation state by introducing BODIPY fluorophore.
TPY, with weak emission but bulky size, is able to
effectively block the thermal decay of TPE (27–29).
Furthermore, within the BODIPY-TPE-TPY ligand (L,
Scheme 1), TPY, as a versatile moiety, was able to
assemble with Zn (II) through coordination-driven self-
assembly to block the π-π stacking of luminogen in the
formation of cyclic dimers, and thus it was able to tune
the emissive properties.
3
3
mixtures.
1
The H NMR signals of D were identified with the aid of
2D NMR study (Figure S11-12). As shown in Figure 1, most
protons of D showed significantly downfield shifts com-
pared to L. For instance, tpy-3ʹ, 5ʹ protons were consider-
ably shifted downfield by approximately δ 0.19, owing to
the loss of electron density upon coordination of the TPY
with metal centres (35, 36). Furthermore, the peaks
assigned to H and H protons of L shifted towards down-
h
k
field by δ 0.27, indicating the electron-withdrawing effect
resulting from coordination. On the contrary, a significant
upshift of tpy-6, 6ʹ′ protons (Δδ = 0.96) could be observed
after coordination with Zn (II), associating with the elec-
1
tron shielding effect (37, 38). The sharp H NMR signals of
D strongly suggested that a discrete and symmetric archi-
tecture was assembled rather than forming supramolecu-
lar polymers.
Result and discussion
The synthesis of ligand L is depicted in Scheme 1.
Utilising two-fold of Suzuki reactions, target L was pre-
pared successfully. The compound 2 (24, 30), compound
A further effort to confirm the formation of D was
conducted by ESI-TOF MS (Figure 2). Based on calcula-
tions, the m/z of 3+ and 4+ charge states would be
1051.3 and 752.2, which correspond to losing 3 and 4
3
(24, 30) and compound 5 (31) were synthesised
according to literature procedures. Briefly, 2 and 3.0
equiv. of N-iodosuccinimide (NIS) were proceeded at
−
PF6 ions, respectively. As expected, the signals of
1
20 °C in chlorobenzene, affording the desired com-
supramolecules in the mass spectrum showed good
agreement with corresponding theoretical isotope
results (Figure 2(a) and Fig. S1). In addition, TWIM-MS
was utilised to address the sizes and shapes of D (39).
As shown in Figure 2(b), the TWIM-MS spectrum of
D revealed one set of signals at each charge state
with narrow drift time distribution, which excluded
the formation of other isomers or conformers.
pound 3 in 70% isolated yield. After that, two consecu-
tive Suzuki cross-coupling reactions were performed to
obtain desired building block L. The first coupling reac-
tion of 1 and 3, followed by adding BF . Et O in one pot
afforded BODIPY-modified precursor 4 with 15% yield.
To prepare the final BODIPY-TPE-TPY ligand, the second
coupling was applied to bridge 4 and 5. The product
3
2

SUPRAMOLECULAR CHEMISTRY
3
Scheme 1. Synthesis of BODIPY-TPE-TPY ligand L.
Scheme 2. Self-assembly of L with Zn(II) to achieve metallocyclic dimer (D).
The modelling structure of D with rigid skeleton is
shown in Figure 3. The width of D is approximately 2.2
nm and the length is around 4.0 nm. As mentioned
earlier, the intramolecular motion of TPE could be
further hindered through RIR by coordination as dis-
played in Figure 3(a). Also, the octahedron coordination

4
Y. YAN ET AL.
1
Figure 1. (colour online) H NMR spectra of L and D (300 K, 500 MHz, CDCl for ligand and 400 MHz, CD CN for supramolecule).
3
3
II
nature of <TPY-Zn -TPY> units along with two bulky
BODIPY groups would block the face-to-face stacking of
supramolecular dimer structures (Figure 3(b)).
We conducted a detailed study of photophysical prop-
erties on L and D after structural characterisation. Based
on the solubility of L, the absorption and fluorescence
spectra were measured in CH Cl (good solvent) with
2
2
different fractions of methanol (poor solvent) at
a concentration of 5.0 μ mol/L. The UV/Vis spectrophoto-
metric studies of L (Fig. S13) revealed that three charac-
teristic absorption band were located at ca. 280 nm, 320
nm and 498 nm, corresponding to TPY, TPE and BODIPY,
respectively. A new absorbance band in the vicinity of 340
2+
nm because of TPY-Zn coordination was attributed to
intramolecular charge transfer (ICT) effect (40). The emis-
sion band of TPE at 420 nm was overwhelmingly sup-
pressed by the BODIPY emission peak at 510 nm when
choosing 325 nm as excitation wavelength (Fig. S16).
Thus, to achieve the optimum excitation efficiency of
L and D, 480 nm was taken as excitation wavelength. As
shown in Figure 4, the emission spectra of L showed an
intense peak at 510 nm with green colour. However, the
fluorescent intensity gradually decreased with the addi-
tion of methanol probably due to the π-π stacking of TPY
units in aggregation state (41, 42). The fluorescence
Figure 2. (colour online) (a) ESI-TOF MS spectrum and (b) TWIM-MS
−
n+.
spectrum of D; The peaks of n+ denote the signals of [D-nPF ]
6

SUPRAMOLECULAR CHEMISTRY
5
Figure 3. (colour online) Representative energy-minimised structure of D (a) top view, (b) side view.
Figure 4. (colour online) (a) Fluorescence spectra (λex = 480 nm, c = 5.0 μM), (b) quantum yields, and (c) photographs of L in CH Cl2
2
/methanol with various methanol fractions.
quantum yields (Φ ) of L in CH Cl /methanol system were
decreased due to poor solvent holdback the luminogen
(fm< 30%) (44). On the contrary, the emission intensity was
rejuvenated by the AIE effect with increasing fractions of
methanol (30%-90%). The variation of the quantum yield
values displayed a similar phenomenon with emission
F
2
2
measured using
a
calibrated integrating sphere.
Correspondingly, quantum yield values were also consis-
tent with the quenching effect. The Φ value of L was
F
gradually decreased from approximately 45% to 7%
because of the ACQ effects on emission intensity.
Indeed, the luminescent efficiency of L in solution was
improved compared with most AIE-fluorophores despite
decreasing during aggregation (11).
intensity (Figure 5(b)). The Φ of D in the acetonitrile/
F
methanol system first decreased slightly and then rose
up with the increasing ratio of methanol. The maximum
Φ value was ca. 12% (80% methanol fraction). We specu-
F
The AIE emission behaviour of D was investigated in
acetonitrile/methanol because it was well dissolved in
acetonitrile but showed low solubility in methanol. As
shown in Figure 5(a), the emission peaks of D were
observed at ca. 510 nm (S0 →S1) and a shoulder emission
at ca. 540 nm (S0 →S2), which are characteristic emission
of BODIPY luminogen (43). In the beginning, upon adding
small fraction of methanol, the emission was slightly
lated that such an emissive behaviour was attributed to
the bulky size of <TPY-Zn -TPY> units (Figure 3), which
inhibited the π-π stacking compared to L.
To further study the emission behaviour of D,
another poor solvent, water was employed instead of
methanol to boost aggregation. However, the AIE beha-
viour revealed in acetonitrile/methanol system van-
ished in the acetonitrile/water system. As shown in
II

6
Y. YAN ET AL.
Figure 5. (colour online) (a) Fluorescence spectra (λex = 480 nm, c = 7.67 μM), (b) quantum yields, and (c) photographs of D in CH3
CN/methanol with various methanol fractions.
Figure 6(a), it revealed that the gradual quenching of
emission intensity resulting from the addition of higher
fractions of water can be owed to dynamic quenching
of D as well as quenching the emission (44–47). As
such, there is a competition between quenching effect
and AIE process in CH CN/water system. The emission
3
(
45). It suggests that water is poor solvent for the
intensity accompanied by quantum yield was gloomy
and decreased to 0% when adding upon 70% water
luminogen, the addition of water results in aggregating
Figure 6. (colour online) (a) Fluorescence spectra (λex = 480 nm, c = 9.59 μM), (b) quantum yields, and (c) photographs of D in CH3
CN/water with various water fractions.

SUPRAMOLECULAR CHEMISTRY
7
Figure 7. TEM images of aggregates D in CH CN/methanol mixtures. (a) and (b) CH CN/methanol = 20%, (c) and (d) CH CN/
3
3
3
methanol = 40%, (e) and (f) CH CN/methanol = 60%, (g) and (h) CH CN/methanol = 80%.
3
3
content (Figure 6(b)). The variation of quantum yield
was consistent with the change of emission intensity.
Compared with the individual building block with
aggregation-caused quenching behaviour, the supra-
molecule exhibited emissive properties in both solution
and aggregation state. With an all-conjugated back-
bone, TPY units could provide additional restriction of
intramolecular rotation through metal coordination.
Moreover, the emissive property of BODIPY was
retained within the supramolecular architecture.
Therefore, this study offers a promising possibility in
the design and development of new emissive materials
through combining multiple fluorophores into one sys-
tem, which could find potential applications in sensing
and imaging.
To investigate aggregation behaviour of D, TEM and DLS
were employed to study the morphology of D in different
CH CN/methanol and CH CN/water mixtures. As revealed
3
3
in Figure 7, D was prone to aggregate into spherical nano-
particles (ca. 10 nm) in the lower fraction of methanol
content (f = 20%). As expected, the size of the spherical
m
nanostructures was increased to ca. 20 nm along with
increasing the fraction of methanol (f = 40%). When 60%
m
of methanol content was reached, the nanospheres were
further aggregated into amorphously botryoid morpholo-
gies. At a high content of methanol (f = 80%), the botryoid
m
aggregates clustered together to produce block-like struc-
tures. As shown in Fig. S17, DLS results exhibited that the
Disclosure statement
average hydrodynamic diameter (D ) of the nanospheres
h
increased from 9.7 nm (f = 20%) to 18.9 nm (f = 40%). At
No potential conflict of interest was reported by the authors.
m
m
higher contents of methanol, nanospheres were further
aggregated into amorphous morphologies, and became
too large to be measured by DLS. The morphological infor-
Funding
mation of D in different CH CN/water mixtures were also
collected as displayed in Figs. S18-19. Compared with the
This research was supported by National Institutes of Health
(R01GM128037)
3
results in CH CN/methanol mixtures, both TEM and DLS
3
results showed that D tended to form larger aggregates
with different fractions of water. These TEM and DLS results
revealed a typical AIE process.
ORCID
Zhan-Hang He
Xiaopeng Li
http://orcid.org/0000-0002-4045-6227
http://orcid.org/0000-0001-9655-9551
Conclusion
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