Tunable Luminescent Lanthanide Supramolecular Assembly Based on Photoreaction of Anthracene

Article abstract of DOI:10.1021/jacs.7b03153

Lanthanide luminescence materials generally show great superiority in light-emitting materials, gaining increasingly exploration in the design of advanced functional materials. Herein, we prepared a supramolecular assembly via the coordination of a host m

Full text of DOI:10.1021/jacs.7b03153

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Communication
Tunable Luminescent Lanthanide Supramolecular
Assembly Based on Photoreaction of Anthracene
Yan Zhou, Heng-Yi Zhang, Zhi-Yuan Zhang, and Yu Liu
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 16 May 2017
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Tunable Luminescent Lanthanide Supramolecular Assembly Based
on Photoreaction of Anthracene
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Yan Zhou,a HengꢀYi Zhang,a,b ZhiꢀYuan Zhang,a and Yu Liu*a,b
aDepartment of Chemistry, State Key Laboratory of ElementoꢀOrganic Chemistry, Nankai University, Tianjin 300071, P. R.
China;
bCollaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071, P. R. China
.
Supporting Information Placeholder
crownꢀ6 (18C6). Despite a variety of research efforts in designing
the smart devices for regulating the luminescence of lanthanide
complexes, more attention has been paid on the single molecule
devices, and designing the reversible stimuliꢀresponsive luminesꢀ
cent dilanthanide supramolecule assembly switches upon a reguꢀ
lable photoreaction remain a considerable challenge. We herein
prepared a supramolecular assembly via the coordination of a new
host molecule (1) and dilanthanide metal. We introduced a 9,10ꢀ
diphenylanthracene (ant) in 1 as a photoꢀresponsive group, which
makes the lowest triplet state of ligand 1 match with the first exꢀ
cited lanthanide state after undergoing photooxygenation of ant
group. We also introduced two terpyridine (tpy) groups as a cheꢀ
lating ligand to coordinate with Tb3+ and Eu3+ ions. In addition,
the existence of two crown ether rings is to prevent the influence
of alkali and alkaline earth metal ions on luminescence of the Ln3+.
The assembly could exhibit excellent lanthanide luminescence
after undergoing a photoreaction from anthracene unit in 1. Moreꢀ
over, control of the photooxygenation process upon light or heat
as inputs enabled the reversible on/off switching of the lanthanide
luminescence.
ABSTRACT: Lanthanide luminescence materials generally
show great superiority in lightꢀemitting materials, gaining increasꢀ
ingly exploration in the design of advanced functional materials.
Herein, we prepared a supramolecular assembly via the coordinaꢀ
tion of a host molecule (1) and dilanthanide metal. Compound 1
possesses a 9,10ꢀdiphenylanthracene (ant) core with photoꢀ
sensitivity and terminal terpyridine (tpy), containing twoꢀarm
dibenzoꢀ24ꢀcrownꢀ8. The assembly could exhibit excellent lanꢀ
thanide luminescence after undergoing a photoreaction from anꢀ
thracene unit in 1. Significantly, the luminescence of the assembly
could be reversibly switched on and off through a regulable phoꢀ
toreaction upon light irradiation or heating. The multiple funcꢀ
tional behavior combined with the ease of assembly reveals that
this photo/thermoꢀcontrolled lanthanide luminescence supramoꢀ
lecular polymer design method offers a convenient pathway for
future engineering of multiꢀstimuliꢀresponsive materials.
Rapidly growing research on stimuliꢀresponsive smart materials
has implications for the development of drug nanocarriers,1 optiꢀ
cal switches,2 data storage,3 optoelectronics devices,4 functional
vesicles,5 superꢀresolution imaging,6 and molecular machines.7
Among the various functional devices, lanthanideꢀluminescenceꢀ
based ones are being increasingly explored in the design of adꢀ
vanced functional materials because of their unique luminescence
properties, such as longꢀlived excited states, sharp lineꢀlike emisꢀ
sion bands, and large Stokes shifts.8 Within the past decade or so,
a number of important breakthroughs have been made in the deꢀ
velopment of lanthanideꢀdoped nanoparticles.9 The most intriꢀ
guing emission property of lanthanide doped nanophosphors is the
upꢀconversion luminescence, which have been mainly used in the
area of optical devices,10 and some of them show considerable
promise for the bioꢀmedical applications.11 Hence, the lanthanide
luminescent materials would be a truly viable choice as active
materials for optoelectronic and sensing devices. With the rapid
development of the lanthanide materials, the reversible modulaꢀ
tion of the luminescent intensity of lanthanide complexes beꢀ
comes one of the most attractive aims in molecular switches.12 We
were also interested in constructing several supramolecular devicꢀ
es including tris[2]ꢀpseudorotaxane13 and [2]pseudorotaxane,14
and demonstrated that they are the excellent reversible luminesꢀ
cent lanthanide molecular switches in the presence of K+ or 18ꢀ
Figure 1. Structures of host compound 1, reference compounds 2
and 3.
The syntheses of 1 and the reference compounds 2 and 3 are
shown in the Supporting Information. Briefly, the 1 was prepared
in 60
%
yield by the Suzuki reaction of 9,10ꢀ
dibromoananthraceneꢀDB24C8 derivative with (4ꢀ([2,2':6',2''ꢀ
terpyridin]ꢀ4'ꢀyl)phenyl)boronic acid under basic conditions,
while compounds 2 and 3 were prepared in 42% and 88% yield,
respectively, according the similar synthesis method to 1.
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Building upon our previous work on luminescent
reverse process can be actuated under thermolysis. If there have
supramolecular devices,13,14 we sought to incorporate the
equimolar Tb3+ and Eu3+ ions into 1 in CHCl3/CH3CN (1:1, v/v).
It is strange that the unique emission properties of Ln3+ ions were
not observed, and the fluorescence of 1 was quenched (Figure 2a).
As we all known, the terpyridine group is an excellent sensitizer
for lanthanide ions, especially Eu3+ and Tb3+ ions.15 So, we
speculate that the synthetic host molecule contains a large
aromatic conjugation system, leading to the properties of the
terpyridine group vary drastically compared with simple
terpyridine group, resulting in a mismatch between the lowest
triplet state of ligand 1 and the first excited lanthanide state. It
means that the host molecule 1 can't be used as an efficient
sensitizer.16 As a result, there is no emission properties of Ln3+ by
addition of Ln3+ into 1. Moreover, the Job analysis of the
fluorescence spectral data (Figure S18) gave the stoichiometric
1:1 binding radio between 1 and Eu3+ ion. Direct morphological
information was provided by transmission electron microscopy
(TEM) observations, showing that compound 1 was the small
nanoparticle morphology (Figure S19a). On the basis of the TEM
analysis, the average diameters of the 1 nanoparticles are about 15
nm. When we added Eu3+ and Tb3+ into 1, the resultant Ln⋅1
complexes formed spherical nanoparticles (Figure S19b). On the
basis of the TEM analysis, the average diameters of the Ln⋅1
spherical nanoparticles are about 170 nm. The DLS results
demonstrated that the main size distribution of the 1/Eu3+ system
was ca. 240 nm, which was basically consistent with the
the substituent groups in the 9,10ꢀpositions of anthracene,
especially alkynylꢀsubstituted or arylꢀsubstituted groups, it tends
to undergo a photooxygenation process. EPOs of anthracenes can
be obtained by the [4 + 2]ꢀcycloaddition with 1O2. The large
substituent groups in the 9,10ꢀpositions of anthracene cause steric
hindrance for photodimerization and favor photooxygenation. We
envisaged that the anthracene unit in 1 will react rapidly to the
corresponding EPO after UV light irradiation.
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1
microscopic investigation results (Figure S19c). In addition, H
NMR spectra of host 1 showed that, after the addition of 1.2 equiv
of Eu(OTf)3, the aromatic HAr protons of tpy moiety were shifted
upfield and downfield, with a serious passivation, while the Hethyl
protons of ethyl groups in DB24C8 ring also changed
correspondingly (Figure S20). These results jointly demonstrated
that Eu3+ was coordinated with 1 to form metalꢀligated species.
The crown ether rings, meanwhile, had some complexing
capacities with Eu3+.
Figure 3. 1H NMR spectra monitoring the reversible photoꢀ
oxygenation of 1 ([1] = 1 mM): (a) before irradiation with UV
light, (b) after irradiation 20 s at 365 nm, (c) after irradiation 100 s
at 365 nm, (d) after irradiation at 365 nm for 100 s and heating at
50 °C for 30 h, and (e) reversible structural transformation of 1 by
irradiation at 365 nm and heating.
To testify this presumption, the host molecule 1 was first irraꢀ
diated at 365 nm under N2 atmosphere. Its 1H NMR spectrum
showed no obvious changes after 1 h irradiation, indicating that
the steric hindrance caused by the phenyl groups in the 9,10ꢀ
positions of anthracene prevented from photodimerization (Figure
S28). When 1 was irradiated at 365 nm in the presence of O2, the
corresponding EPO product was undoubtedly obtained. Accordꢀ
ingly, UVꢀvis absorption measurements, fluorescence spectrum,
1
MALDIꢀTOFꢀMS, and H NMR were performed to monitor the
photooxygenation process of anthracene. The absorption of the
anthracene moiety in the range of 350 ꢀ 420 nm vanished comꢀ
pletely after irradiation by UV light at 365 nm for 100 s, implying
that the anthracene chromophore had quantitatively been changed
(Figure S29a). Comparatively, the corresponding emission spectra
of 1 (λex = 365 nm) showed a decrease in intensity at 500 nm with
the concomitant appearance of peak at 428 nm after 100 s of irraꢀ
diation at 365 nm, indicating that the anthracene chromophore
1
photoreacted (Figure S29b). H NMR spectroscopy is a powerful
tool to determine the reversible photooxygenation process. As
shown in Figure 4, the proton signals of Ha at 6.82 ppm assigned
to the protons of ant group in 1 displayed a upfield shift after UV
light irradiation (λirr = 365 nm, tirr = 100 s). While the proton sigꢀ
nals of Hb at 7.61 ppm assigned to the protons of benzene in tpy
group displayed a downfield shift. These results indicated the
conversion of ant group to EPO one. In addition, when the EPO
was heated at 50 °C for 30 h, a full reconversion to the parent
Figure 2. Emission spectra variation of (a) 1 ([1] = 0.01 mM)
upon addition of Eu3+ or Tb3+ (λex = 365 nm), (b) Eu⋅2, (c) Tb⋅2,
and (d) EuTb⋅2 (λex = 290 nm) ([2] = 0.01 mM). Inset photo
image of fluorescence changes of 1 and 2 upon addition of Eu3+ or
Tb3+ in CH3CN/CHCl3 (1:1, v/v) solution.
It is wellꢀdocumented that anthracenes are photoresponsive and
transform into dimerization under UV light irradiation.17 In
addition, anthracene can also trap singlet oxygen and form stable
endoperoxides (EPOs),18 which process is reversible and the
1
species 1 occurred, as confirmed by H NMR spectroscopy (Figꢀ
ure 3d). Moreover, MALDIꢀTOFꢀMS was performed to monitor
the photooxygenation process (Figure S30). By these results, we
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confirmed that the ant core within the host molecule could underꢀ
tory luminescence in solution. When excited at 320 nm, the comꢀ
plex showed five sharp emission peaks, at 541 nm (5D0 → 7F0),
go reversible photooxygenation between ant (thermolysis) and
EPO (λ = 365 nm irradiation), which can be utilized for further
functional explorations.
590 nm (5D0 → 7F1), 615 nm (5D0 → 7F2), 648 nm (5D0 → 7F3),
and 684 nm (5D0 →7F4) (Figure 4a). The fluorescence of Eu⋅1EPO
may be attributed to intramolecular energy transfer (ET) from the
excited tpy moiety to Eu3+.
Similar changes in fluorescence spectra were also observed in
the case of Tb3+ ion. The emission spectra of Tb⋅1EPO exhibited
sharp bands at 489 nm, 544 nm, 584 nm and 620 nm (Figure 4b).
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They were assigned to the D4 → 7F6, D4 → 7F5, D4 → 7F4 and
5D4 → 7F3 transition of Tb3+, respectively. The quantum yield
(QY) upon excitation at 320 nm was 12.4% for Eu⋅1EPO and 4.2%
for Tb⋅1EPO, suggesting that the luminescence of the assembly
could be modulated by a photoreaction. Moreover, when equimoꢀ
lar Tb3+ and Eu3+ ions were simultaneously added into 1EPO, the
bimetallic EuTb⋅1EPO showed strong paleꢀyellowꢀemissive (Figure
4c). With the help of their luminescent proporties, we determined
the stoichiometry of Tb versus Eu in EuTb1EPO by integrating the
Tb3+ (7F6) and the Eu3+ (7F4) transitions,19 and the obtained value
of Tb:Eu is about 4:1. We also further explored the morphological
information of the Ln⋅1EPO nanoarchitecture using TEM observaꢀ
tions. The complex Ln⋅1EPO revealed the nanofibrous morphology
(Figure S31), while the spherical nanoparticles were also found,
indicating a possible secondary aggregation of linear assemblies
into spheres by the coiling. We also embedded the Ln⋅1EPO comꢀ
plexes into poly(methyl methacrylate) (PMMA). The spinꢀcoated
films were found to exhibit excellent and characteristic lanthanide
luminescence in the solid state similar to that observed in solution
(Figure S32 ꢀ S33), indicative of utmost importance to their pracꢀ
tical applications. Intriguingly, the existence of crown ether ring
in this system could effectively prevent the influence of alkali and
alkaline earth metal ions on luminescence of Ln3+, especially for
Ba2+(Figure S34). To some extent, the fluorescence intensity of
Ln3+ increased obviously after adding the alkali and alkaline earth
metal ions. The results suggested that the existence of crown ether
ring in this system could bind with the alkali and alkaline earth
metal ions, which may lead to the structure immobilization of the
supramolecular assembly, accompanied by an increase of the riꢀ
gidity of the assembly, which jointly cause an increase of the fluoꢀ
rescence intensity of Ln•1EPO. Furthermore, we synthesized one
reference compound 2 with a nonꢀconjugation link between ant
and tpy, and one terminal terpyridine compound 3. The control
experiments using 2 and 3 were performed, respectively. The
results obtained indicate that there exists the intramolecular enerꢀ
gy transfer (ET) from the excited terpyridine moiety of 2 or 3 to
Ln3+,20 leading to neither Ln⋅2 nor Ln⋅3 being used to switch
on/off the luminescence. Therefore, it is necessary to design both
a conjugation system of ant with tpy and the dilanthanide metal
polyꢀcomplex.
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5
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Figure 4. Emission spectra of (a) Eu⋅1EPO, (b) Tb⋅1EPO, (c)
EuTb⋅1EPO and emission intensity changes after heating 30 h (λex
= 320 nm). Inset photo image of fluorescence changes of 1EPO
upon addition of Eu3+ or Tb3+ in CH3CN/CHCl3 (1:1, v/v) solution,
and then heating 30 h.
Scheme 1. Schematic Illustration of the Lanthanide Lumines-
cence Driven by the Process of Reversible Photoreaction.
The above results suggested that host molecule could retain
partial structural integrity upon UVꢀtriggered antꢀtoꢀEPO transiꢀ
tion (Figure 3). The EPOꢀform host molecular, arisen from UV
irradiation with O2, still contains terminal tpy groups. Therefore,
1EPO would be combined with Ln3+ ion to afford a metallosupraꢀ
molecular assembly. Interaction of 1EPO with Eu3+ ions was studꢀ
ied in CHCl3/CH3CN (1:1, v/v) solution by adding Eu3+ to 1EPO
with a tpy:Eu3+ ratio of 2:1. Benefiting from the excellent lumiꢀ
nescence properties of Eu3+, complex Eu⋅1EPO displayed satisfacꢀ
The reversible photooxygenation process of anthracene unit in
1 further enabled us to modulate the luminescence of the
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Schneebeli, S. T.; Li, H.; Vermeulen, N. A.; Ke, C.; Stoddart, J. F.
Nat. Nanotechnol. 2015, 10, 547ꢀ553. (c) Kay, E. R.; Leigh, D. A.
Angew. Chem. Int. Ed. 2015, 54, 10080ꢀ10088.
assembly. Intriguingly, as shown in Figure 4, the characteristic
fluorescence emission of the assembly was significantly quenched
upon EPOꢀtoꢀant transition after heating the Ln⋅1EPO for 30 h.
Briefly, the supramolecular assembly could exhibit the expected
luminescent lanthanide switching behavior through reversible antꢀ
toꢀEPO transition. Scheme 1 shows the switch modes of the
assembly, which exhibits the expected luminescent lanthanide
switching behavior.
8. (a) Carr, P.; Evans, N. H.; Parker, D. Chem. Soc. Rev. 2012, 41, 7673ꢀ
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9
In summary, a photoreaction tunable reversible lanthanide luꢀ
minecence supramolecular assembly was successfully constructed
through the host molecule 1 and dilanthanide metal. Significantly,
the existence of crown ether ring in this system could effectively
prevent the influence of alkali and alkaline earth metal ions on
luminescence of the Ln⋅1EPO, and the lanthanide luminescence of
assembly could be reversibly responsive through a regulable phoꢀ
toreaction upon light irradiation or heating. The photo/thermoꢀ
stimuliꢀdriven luminescent lanthanide molecular switch augurs
well for their future in multistimulusꢀdriven molecular machines
and logic gates applications.
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ne, F.; Cerruti, M. J. Am. Chem. Soc. 2016, 138, 1078ꢀ1083. (b)
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ASSOCIATED CONTENT
Supporting Information.
14. Ding, Z. ꢀJ.; Zhang, Y. ꢀM.; Teng, X.; Liu, Y. J. Org. Chem. 2011,
76, 1910ꢀ1913.
Compound characterization, and additional figures in the optical
experiments are provided. This material is available free of charge
via the Internet at http://pubs.acs.org.
15. (a) Kotova, O.; Daly, R.; dos Santos, C. M.; Boese, M.; Kruger, P. E.;
Boland, J. J.; Gunnlaugsson, T. Angew. Chem. Int. Ed. 2012, 51,
7208ꢀ7212. (b) Chen, P.; Li, Q.; Grindy, S.; HoltenꢀAndersen, N. J.
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AUTHOR INFORMATION
16. (a) Steemers, F. J.; Verboom, W.; Reinhoudt, D. N.; van der Tol, E.
B.; Verhoeven, J. W. J. Am. Chem. Soc. 1995, 117, 9408ꢀ9414. (b)
Bünzli, J. C. G.; Piguet, C. Chem. Soc. Rev. 2005, 34, 1048ꢀ1077.
Corresponding Author
yuliu@nankai.edu.cn.
17. (a) Yamamoto, T.; Yagyu, S.; Tezuka, Y. J. Am. Chem. Soc. 2016,
138, 3904ꢀ3911. (b) Murray, D. J.; Patterson, D. D.; Payamyar, P.;
Bhola, R.; Song, W.; Lackinger, M.; Schlüter, A. D.; King, B. T. J.
Am. Chem. Soc. 2015, 137, 3450ꢀ3453.
ACKNOWLEDGMENT
We thank NNSFC (21432004, 21372128 and 91527301), and the
973 Program (2015CB856500) for financial support
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15082. (b) Filatov, M. A.; Karuthedath, S.; Polestshuk, P. M.; Savoie,
H.; Flanagan, K. J.; Sy, C.; Sitte, E.; Telitchko, M.; Laquai, F.;
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