Intrinsic self-trapped broadband emission from zinc halide-based metal-organic frameworks

Article abstract of DOI:10.1039/d0cc07320b

Organolead halide perovskites are an emerging class of intrinsic self-trapped broadband emitters, but suffer from lead toxicity and stability problems. Herein, we report a series of metal-organic frameworks (MOFs) based on 0-D zinc halide secondary building units (SBUs), which emit large Stokes shifted broadband bluish-white light. A variety of photophysics studies demonstrate that the broadband emission probably originates from self-trapped excitons, owing to the structurally deformable SBUs. Among the intrinsic self-trapped emitters, these MOFs are very rare examples that exhibit both long-term environmental stability and contain non-toxic elements. Moreover, the open porosity enables the MOF to serve as a host matrix for encapsulating green-emitting Alq3 molecules, exhibiting cold white-light chromatic coordinates of (0.27,0.36) and a correlated color temperature of 8321 K.

Full text of DOI:10.1039/d0cc07320b

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: W. Ma, X. Song, J.
Yin and H. Fei, Chem. Commun., 2021, DOI: 10.1039/D0CC07320B.
Volume 54
Number
January 2018
Pages 1-112
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
1
4
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Page 1 of 5
Please d oC hn eo mt Ca do mj u ms t margins
View Article Online
DOI: 10.1039/D0CC07320B
COMMUNICATION
Intrinsic Self-Trapped Broadband Emission from Zinc Halide-
Based Metal-Organic Frameworks
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a,
Wen Ma, Xueling Song, Jinlin Yin, and Honghan Fei *
DOI: 10.1039/x0xx00000x
Organolead halide perovskites are an emerging class of intrinsic lead halide frameworks, demonstrating robustness over a wide
1
1-15
self-trapped broadband emitters, but suffer from lead toxicity range of pH as well as aqueous boiling condition.
However,
and stability problems. Herein, we report a series of metal- the lead toxicity problem must be solved for WLED
organic frameworks (MOFs) based on 0-D zinc halide secondary applications. It is highly important to construct lead-free,
1
6-19
building units (SBUs), which emit large Stokes shifted water-stable metal halide materials.
broadband bluish-white light. A variety of photophysics studies Metal-organic frameworks (MOFs) incorporating multiple
demonstrate the broadband emission probably originate from luminescent centers is a promising platform to achieve white-
2
0-22
self-trapped excitons, owing to the structurally deformable SBUs. light emission.
The porosity of open frameworks allows for
Among the intrinsic self-trapped emitters, these MOFs are very precise tuning of luminescence by introduction of guest-based
2
2
rare examples to occupy both long-term environmental stability emission center.
So far, the vast majority of white-light-
and non-toxic elements. Moreover, the open porosity serve the emissive MOFs are based on emissions from several rare-earth
3
+
MOF as a host matrix for encapsulating green-emitting Alq3 metal ions (e.g. Ln ) despite the self-absorption problems as
2
3,24
molecules, exhibiting cold white-light chromatic coordinates of well as overwhelming demands for rare earth elements.
(
0.27,0.36) and correlated color temperature of 8321 K.
Broadband white-light emission from non-rare-earth MOFs
often arise from ligand-based photoluminescence (PL) and/or
charge transfer between metal nodes and linkers
White light-emitting diodes (WLEDs), the next-generation
2
4-26
candidate in solid-state lighting technology, have attracted great
attentions owing to their high energy-efficiency and long-term
stability.
combining blue InGaN LEDs and yellow-emitting phosphors
(
including self-absorption and colour aging.
desirable to develop an UV-excited single-component
broadband white-light emitting phosphor.
(
MLCT/LMCT).
Very few MOFs exhibit broadband white-
light emission originating only from the inorganic building
1
, 2
2+
2+
The conventional approach to assemble WLEDs is
blocks, until our very recent findings in Pb /Cd halide-based
MOFs with structurally deformable secondary building units
3
+
1
2,15,27
e.g. Y Al O :Ce ), which suffer a variety of drawbacks
3 5 12
(SBUs).
In contrast to lead perovskites, this class of
3, 4
Thus, it is highly
single-source, broadband white-light emitters have many
intriguing attributes including introduction of guest molecules
and facile functionalization of photoactive species.
5, 6
Recently, organolead halide perovskites are an emerging
class of intrinsic broadband white-light phosphors, resulting
from self-trapped excitons in the deformable lattice.
Herein, we have studied the intrinsic broadband emission
2+
6+
from a series of Zn -based MOFs based on [Zn X ]
5
4
7
-10
(
X=Cl/Br/I) as SBUs and bis(1H-1,2,3-triazolo[4,5-b],[4’,5’-
Lowering the inorganic dimensionality to 0-D is an effective
strategy to enhance the photoluminescence quantum efficiency
i])dibenzo[1,4]dioxin (H BTDD) as organic linkers. A variety
2
of variable-temperature photophysics studies indicate the large
Stokes shifted emission probably originate from self-trapped
excitons. Moreover, the green-emitting tris(8-hydroxyquinoline)
aluminium(III) (Alq3) molecules have been successfully
incorporated into the MOF porosity, achieving cold white-light
emission with Commission Internationale de l’Eclairage (CIE)
chromatic coordinates of (0.27, 0.36) and correlated colour
temperature (CCT) of 8321 K.
(
PLQE), owing to the strong exciton confinement and
populated self-trapped states. However, the hydrophilic nature
of organoammonium cations in many perovskites affords them
to be susceptible to hydrolysis even under ambient conditions.
Our group have employed anionic organocarboxylates (instead
of organoammonium cations) to template a class of cationic
Zn Cl BTDD (MFU-4l(Zn)-Cl), consisting of 6-connected
5
4
+
3
Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of
Chemical Science and Engineering, Tongji University, 1239 Siping Rd.,
Shanghai 200092, P. R. China. E-mail: fei@tongji.edu.cn
6
2-
[Zn
Cl
]
4
nodes and BTDD struts, was chosen because of its
5
high chemical stability and non-toxic metal (Fig. 1a and b).
MFU-4l(Zn)-Cl was synthesized under solvothermal conditions
†
Electronic supplementary information (ESI) available: Experimental details and
additional characterization. See DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 2 of 5
COMMUNICATION
Journal Name
Valence band
View Article Online
DOI: 10.1039/D0CC07320B
maximum (VBM) of three
materials were measured
to be 2.98 eV for MFU-
4l(Zn)-Cl, 2.28 eV for the
bromide analog and 1.98
eV for the iodide analog,
respectively, by linearly
extrapolating the low-
binding-energy edge of
X-ray
photoelectron
spectroscopy (Fig. S8,
ESI†).
dependent
consistent with the trend
of organolead halide
perovskites.
UV-vis
The halide-
VBM is
2
+
6+
Fig. 1 (a,b) Crystallographic view of two crystallographic independent Zn in [Zn Cl ] nodes,
5
4
2
+
2+
octahedral coordinated Zn
(blue) (a) and tetrahedral coordinated Zn
(turquoise) (b); (c)
crystallographic view of MFU-4l(Zn)-Cl along the a-axis; (c) simulated X-ray diffraction (XRD) pattern
of MFU-4l(Zn)-Cl and powder X-ray diffraction (PXRD) patterns of synthesized MFU-4l(Zn)-X (X = Cl,
Br, I). Zn turquoise, Cl green, N blue, O red, C grey, yellow spheres represent the void inside the cages.
Hydrogen atoms are omitted for clarity.
However,
absorption
show
spectroscopy
analogous band gap of
3.39 eV (366 nm) for
MFU-4l(Zn)-Cl, 3.62 eV (364 nm) for MFU-4l(Zn)-Br and
using anhydrous ZnCl2 and H BTDD in DMF at 145 °C,
according to the previous literature.
2
2
8
The resultant material has no N-H stretching vibration 3.43 eV (362 nm) for MFU-4l(Zn)-I, respectively, presumably
-
1
(
~3200 cm ) in fourier-transform infrared spectroscopy (FTIR), owing to the absorption from the conjugated triazolate-based
suggesting the complete conversion of H BTDD (Fig. S2, ligand (Fig. S9 and S10, ESI†). Upon 365 nm excitation at
2
ESI†). Activated MFU-4l(Zn)-Cl exhibits a characteristic type- room temperature, both as-synthesized MFU-4l(Zn)-Cl and
I sorption behaviour, corresponding to the microporous nature. MFU-4l(Zn)-Br exhibit broadband bluish white-light with
The Brunauer-Emmett-Teller (BET) surface area is calculated emission centered at 467 and 466 nm, respectively (Fig. 2a and
3
to be 3096.55 cm /g, measured with N sorption isotherm at 77 b). Although the large Stokes shifts of ~100 nm is slightly
2
K (Fig. S4, ESI†).
lower than emission from organolead halide materials, these
1
0
Importantly, the isoreticular synthesis of the bromide and values are often the cases in self-trapped emission from d
2
9, 30
iodide analogs were successful when using ZnBr or ZnI in metal-based perovskites.
The iodide analog shows a
2
2
place of ZnCl2 during solvothermal synthesis.
Both PXRD and elemental analysis evidence the
high phase purity of MFU-4l(Zn)-Br and MFU-
4
l(Zn)-I (Fig. 1d and experimental Section in
ESI†). Indeed, all three materials show well-
defined cubic microcrystalline morphology by
scanning electron microscopy (SEM) (Fig. S3,
ESI†). A reasonable decrease of BET surface
3
area from 3096.55 cm /g (MFU-4l(Zn)-Cl) to
3
2
669.95 cm /g (MFU-4l(Zn)-Br) and 2259.68
3
cm /g (MFU-4l(Zn)-I) was observed (Fig. S4,
ESI†). The as-synthesized MFU-4l(Zn)-X
X=Cl/Br/I) demonstrate high chemical stability
(
in both aqueous condition and common organic
solvents (e.g. EtOH, DCM, and DMF). No
significant loss in both crystallinity decrease and
mass balance after incubating the MOFs in these
solvents for 24 h (Fig. S5, ESI†). The important
moisture stability overcomes the hydrolysis
problems in organolead halide perovskites.
Thermogravimetric analysis (TGA) and ex-situ
thermodiffraction again indicate the high thermal
stability of MFU-4l(Zn) up to 350 °C (Fig. S6
and S7, ESI†).
Fig. 2 Absorption (black) and room temperature emission spectra of MFU-4l(Zn)-
Cl (a, red), MFU-4l(Zn)-Br (b, blue) and MFU-4l(Zn)-I (c, green); (d) CIE
chromaticity coordinates of MFU-4l(Zn).
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Please d oC hn eo mt Ca do mj u ms t margins
Journal Name
COMMUNICATION
View Article Online
DOI: 10.1039/D0CC07320B
Fig. 4 (a) Normalized emission spectra of different degree of
functionalized Alq3@MFU-4l(Zn)-Br; (b) CIE chromaticity
coordinates of different degree of functionalized Alq3@MFU-
4
l(Zn)-Br. PL measurements were performed upon 365 nm
excitation.
7
7 K (Fig. 3c), which evidences the self-trapped emission
Fig. 3 (a,b) Excitation-dependent (a) and temperature-dependent
b) emission spectra of MFU-4l(Zn)-Br; (c) photoluminescence
decay of MFU-4l(Zn)-Br at room temperature (monitored at 340
nm); (d) configuration coordinate diagram for the structural-
deformation-induced large Stokes-shift broadband emission.
arising from strong electron-phonon coupling. The presence of
-D inorganic building units with high structural strain often
(
0
contain strongly localized excitons, which further induce highly
distorted sub-lattice and strong electron-phonon coupling.
34
10, 33,
Assuming the harmonic lattice vibration, the phonon energy
can be estimated from the temperature-dependent FWHM by
7
,8,35
following equation:
+ 훤퐿푂ꢀ푒퐸ꢁꢂ/푘 ꢃ − 1ꢄ + 훤ꢇ푛ℎ푒ꢅ퐸
훤(푇) = 훤
sharper emission centered at 433 nm probably owing to the
weaker structural deformation, which has been commonly
observed in lead iodide perovskites (Fig. 2c).
ꢅꢆ
퐵
푏 퐵
/푘 ꢃ
(1)
0
8, 31
Importantly, where Г is the FWHM of the broadband emission when T = 0
0
H BTDD ligand shows a different emission with two PL K, ΓLO and Γinh represent the contribution of electron−phonon
2
maxima at 390 and 510 nm, resulting from the n-π* electronic coupling and inhomogeneous broadening of the FWHM. The
transitions in triazolate ligands (Fig. S11, ESI†). This study best fit (see fitting details in Fig. S17, ESI†) indicates ΓLO of
suggests the broadband emission of MFU-4l(Zn) originate from 126(7) meV and phonon energy (ELO) of 25(3) meV,
metal-halide SBUs.
corresponding to the Raman-active Zn-Br frequency of 212
−
1
The photoemission afford Commission Internationale de cm (Fig. S18, ESI†). Thus, these advanced photophysics
l’Eclairage (CIE) chromatic coordinates of (0.22,0.27) for studies indicate the broadband emission probably originate
MFU-4l(Zn)-Cl, (0.19,0.23) for MFU-4l(Zn)-Br, and (0.17,0.14) from self-trapped excitons (e.g. dimerized Zn species, Zn –
3+
2+
2
2+
for MFU-4l(Zn)-I, respectively, corresponding to the so-called Zn distance of 3.64 Å) in deformable SBUs.
cold” white-light emission (Fig. 2d and Fig. S12, ESI†). The
In order to achieve white-light emission, we sought to
“
highest external PLQE of the three materials reaches 3.2% for investigate the incorporation of luminescence guest molecules
the bromide analog, while the chloride and iodide have PLQE into the MOF porosity. Since MFU-4l(Zn)-Br occupying two
of ~1% (Table S1, ESI†). Notably, all of the three MFU-4l(Zn) different pore cages with ~15 Å and 12 Å in diameter, Alq3
exhibit stable PL upon continuous irradiation (365 nm, 4 W) complexes with efficient green emission and suitable molecule
under ambient condition for up to 7 days (Fig. S13, ESI†). size (9 Å) were chosen to be encapsulated in the MOF.
Moreover, no obvious change in both PL intensity and Treatment of Alq3 was performed by introducing 10 mg MFU-
broadening of the emission have been noticed after chemical 4l(Zn)-Br into a 10 mL DMF solution containing 1 mg Alq3.
treatment in different solvents (e.g. DMF, H O and EtOH) for After incubating the mixture at room temperature for a certain
2
o
2
4 h and thermal treatment in air up to 350 C (Fig. S14~S16, period of time (i.e. 0.5, 1.5 and 3 h), the Alq3 degree of
ESI†).
functionalization reaches 1.7 wt%, 2.1 wt% and 2.5 wt%,
Given the high robustness and broadband emission of respectively (Table S2, ESI†). PXRD patterns and FTIR
MFU-4l(Zn), we continue to investigate the PL mechanism. spectra indicate the post-functionalized MOFs retain the parent
First, no obvious change was observed from the excitation- framework (Fig. S19 and S20, ESI†). SEM images reveal
dependent PL from 290 nm to 365 nm excitation, agreeing with Alq3@MFU-4l(Zn)-Br retaining the cubic microcrystalline
the claim of intrinsic self-trapped emission (Fig. 3a). Moreover, morphology after Alq3 treatment (Fig. S21, ESI†). Energy-
the time-resolved photoluminescence decay study indicates a dispersive X-ray spectroscopy (EDS) elemental mapping
short PL lifetime of 2.34 ns for MFU-4l(Zn)-Br, which resides confirm the homogeneous distribution of Alq3 molecules in the
3
2
well in the range of self-trapped excitons (Fig. 3b).
The porosity of MFU-4l(Zn)-Br (Fig. S22, ESI†). Meanwhile, N2
temperature-dependent PL study demonstrates sharper emission absorption isotherm suggest a moderate decrease of BET
3
and higher intensity when temperature decreasing from 378 to surface are from 2669.95 cm /g (MFU-4l(Zn)-Br) to 2250.86
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 4 of 5
COMMUNICATION
Journal Name
3
cm /g (2.5% Alq3@MFU-4l(Zn)-Br), suggesting the successful 11. Z. Zhuang, C. Peng, G. Zhang, H. Yang, J. Yin and H. Fei,
View Article Online
Angew. Chem., Int. Ed., 2017, 56, 14411D-1O4I4: 1106..1039/D0CC07320B
2. C. Peng, Z. Zhuang, H. Yang, G. Zhang and H. Fei, Chem. Sci.,
encapsulation of Alq3 in the porosity of MFU-4l(Zn)-Br (Fig.
S23 and S24, ESI†). Upon 365 nm UV irradiation, the MOFs
exhibit tunable white-light emission with CIE coordinates from
1
2
018, 9, 1627-1633.
1
1
3. J. Yin, H. Yang and H. Fei, Chem. Mater., 2019, 31, 3909-3916.
4. C. Peng, X. Song, J. Yin, G. Zhang and H. Fei, Angew. Chem.,
Int. Ed., 2019, 58, 7818-7822.
(
0.19, 0.23) for MFU-4l(Zn)-Br to (0.27, 0.36) for 2.5%
Alq3@MFU-4l(Zn)-Br (Fig. 4 and Fig. S25, ESI†). The latter
is close to (0.33, 0.33) of the pure white light, corresponding to 15. X. Song, C. Peng, X. Xu, J. Yin and H. Fei, Chem. Commun.,
2
020, 56, 10078-10081.
CCT of 8321 K. PL excitation of Alq3 is centered at 462 nm
and resides well in the broadband emission of MFU-4l(Zn)-Br,
suggesting the electron transfer process between Alq3 and
MFU-4l(Zn)-Br (Fig. S26, ESI†). Again, the process is further
confirmed by the longer PL lifetime of MFU-4l(Zn)-Br with
encapsulated Alq3 increasing from 1.7 wt% to 2.5 wt% (Table
S2 and Fig. S27, ESI†).
1
1
1
6.L. Zhou, J. F. Liao, Z. G. Huang, X. D. Wang, H. Y. Chen and D.
B. Kuang, Angew. Chem., Int. Ed., 2019, DOI:
1
7.L. J. Xu, H. Lin, S. Lee, C. Zhou, M. Worku, M. Chaaban, Q. He,
A. Plaviak, X. Lin, B. Chen, M.-H. Du and B. Ma, Chem. Mater.,
2020, 32, 4692-4698.
8. I. Spanopoulos, I. Hadar, W. Ke, P. Guo, S. Sidhik, M.
Kepenekian, J. Even, A. D. Mohite, R. D. Schaller and M. G.
Kanatzidis, J. Am. Chem. Soc., 2020, 142, 9028-9038.
9. Y. Liu, Y. Jing, J. Zhao, Q. Liu and Z. Xia, Chem. Mater., 2019,
0.1002/anie.201907503.
In conclusion, we report three new members of intrinsic
6+
broadband light-emissive MOFs based on 0-D [Zn X ]
5
4
1
2
2
2
(
X=Cl/Br/I) SBUs, overcoming the lead toxicity problems in
3
1, 3333-3339.
many lead halide-based white-light phosphors. In addition, the
chemical robust nature of MFU-4l(Zn) achieves undiminished
photoemission upon continuous UV irradiation under ambient
condition (~60% RH). The open porosity of MFU-4l(Zn)
provide an excellent platform to encapsulate Alq3 as a second
emission center to further tune the PL. We believe this study
significantly advances the advantages of MOFs (e.g. porosity,
stability and non-toxic metal) into the field of lead halide self-
trapped white-light emitters.
0. Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev., 2012, 112,
1126-1162.
1. M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk,
Chem. Soc. Rev., 2009, 38, 1330-1352.
2. C. Y. Sun, X. L. Wang, X. Zhang, C. Qin, P. Li, Z. M. Su, D. X.
Zhu, G. G. Shan, K. Z. Shao, H. Wu and J. Li, Nat. Commun.,
2
013, 4, 2717.
2
3. T. Mondal, S. Mondal, S. Bose, D. Sengupta, U. K. Ghorai and S.
K. Saha, J. Mater. Chem. C, 2018, 6, 614-621.
24. Y. Cui, B. Chen and G. Qian, Coordin. Chem. Rev., 2014, 273-
74, 76-86.
2
This work was supported by grants from the National
Natural Science Foundation of China (21971197 and
2
5. M. S. Wang, S. P. Guo, Y. Li, L. Z. Cai, J. P. Zou, G. Xu, W. W.
Zhou, F. K. Zheng and G. C. Guo, J. Am. Chem. Soc., 2009, 131,
1
6. D. F. Sava, L. E. Rohwer, M. A. Rodriguez and T. M. Nenoff, J.
Am. Chem. Soc., 2012, 134, 3983-3986.
51772217),
the
Shanghai
Rising-Star
Program
3572-13573.
(
No.20QA1409500), the Recruitment of Global Youth Experts
2
by China and the Science & Technology Commission of
Shanghai Municipality (19DZ2271500).
27.G. Zhang, J. Yin, X. Song and H. Fei, Chem. Commun., 2020, 56,
325-1328.
1
2
8. D. Denysenko, M. Grzywa, M. Tonigold, B. Streppel, I. Krkljus,
M. Hirscher, E. Mugnaioli, U. Kolb, J. Hanss and D. Volkmer,
Chem. Eur. J., 2011, 17, 1837-1848.
Conflicts of interest
There are no conflicts to declare.
2
3
9. T. D. Creason, T. M. McWhorter, Z. Bell, M. H. Du and B.
Saparov, Chem. Mater., 2020, 32, 6197-6205.
0.C. Sun, Y. H. Guo, Y. Yuan, W. X. Chu, W. L. He, H. X. Che, Z.
H. Jing, C. Y. Yue and X. W. Lei, Inorg. Chem., 2020, 59, 4311-
Notes and references
4
319.
1
2
. E. F. Schubert and J. K. Kim, Science, 2005, 308, 1274-1278.
. S. Pimputkar, J. S. Speck, S. P. DenBaars and S. Nakamura, Nat.
Photonics, 2009, 3, 180-182.
3
1. D. Cortecchia, S. Neutzner, A. R. Srimath Kandada, E. Mosconi,
D. Meggiolaro, F. De Angelis, C. Soci and A. Petrozza, J. Am.
Chem. Soc., 2017, 139, 39-42.
2. A. Yangui, R. Roccanova, T. M. McWhorter, Y. Wu, M. H. Du
and B. Saparov, Chem. Mater., 2019, 31, 2983-2991.
3. L. Mao, P. Guo, M. Kepenekian, I. Hadar, C. Katan, J. Even, R.
D. Schaller, C. C. Stoumpos and M. G. Kanatzidis, J. Am. Chem.
Soc., 2018, 140, 13078-13088.
4. C. Zhou, H. Lin, Y. Tian, Z. Yuan, R. Clark, B. Chen, L. J. van
de Burgt, J. C. Wang, Y. Zhou, K. Hanson, Q. J. Meisner, J. Neu,
T. Besara, T. Siegrist, E. Lambers, P. Djurovich and B. Ma,
Chem. Sci., 2018, 9, 586-593.
3
4
. S. Nakamura, Angew. Chem., Int. Ed., 2015, 54, 7770-7788.
. M. Shang, C. Li and J. Lin, Chem. Soc. Rev., 2014, 43, 1372-
3
3
1
386.
5
6
. Y. W. Zhao, F. Q. Zhang and X. M. Zhang, ACS Appl. Mater.
Interfaces, 2016, 8, 24123-24130.
. L. Wang, W. Li, L. Yin, Y. Liu, H. Guo, J. Lai, Y. Han, G. Li, M.
Li, J. Zhang, R. Vajtai, P. M. Ajayan and M. Wu, Sci. Adv., 2020,
3
3
6
, eabb6772.
7
8
9
1
. E. R. Dohner, E. T. Hoke and H. I. Karunadasa, J. Am. Chem.
Soc., 2014, 136, 1718-1721.
. E. R. Dohner, A. Jaffe, L. R. Bradshaw and H. I. Karunadasa, J.
Am. Chem. Soc., 2014, 136, 13154-13157.
. J. Li, J. Wang, J. Ma, H. Shen, L. Li, X. Duan and D. Li, Nat.
Commun., 2019, 10, 806.
0. Z. Yuan, C. Zhou, Y. Tian, Y. Shu, J. Messier, J. C. Wang, L. J.
van de Burgt, K. Kountouriotis, Y. Xin, E. Holt, K. Schanze, R.
Clark, T. Siegrist and B. Ma, Nat. Commun., 2017, 8, 14051.
5. J. Lee, E. S. Koteles and M. O. Vassell, Phys. Rev. B, 1986, 33,
5
512-5516.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC07320B
Table of Content
MFU-4l(Zn) are a class of non-toxic metal-based intrinsic self-trapped broadband emitters,
which have high stability and can be functionalized by luminescent Alq3 guests.