Highly Luminescent Copper Iodide Cluster Based Inks with Photoluminescence Quantum Efficiency Exceeding 98%

Article abstract of DOI:10.1021/jacs.9b12908

Highly luminescent inks are desirable for various applications such as decorative coating, art painting, and anticounterfeiting, to name a few. However, present inks display low photoluminescent efficiency requiring a strong excitation light to make them glow. Here, we report a highly luminescent ink based on the copper-iodide/1-Propyl-1,4-diazabicyclo[2.2.2]octan-1-ium (Cu₄I₆(pr-ted)₂) hybrid cluster with a quantum efficiency exceeding 98%. Under the interaction between the Cu₄I₆(pr-ted)₂ hybrid cluster and polyvinylpyrrolidone (PVP), the highly luminescent Cu₄I₆(pr-ted)₂/PVP ink can be facilely prepared via the one-pot solution synthesis. The obtained ink exhibits strong green light emission that originates from the efficient phosphorescence of Cu₄I₆(pr-ted)₂ nanocrystals. Attractively, the ink displays high conversion efficiency for the ultraviolet light to bright green light emission due to its wide Stokes shift, implying great potential for anticounterfeiting and luminescent solar concentrator coating.

Full text of DOI:10.1021/jacs.9b12908

Subscriber access provided by UNIV OF CAMBRIDGE
Communication
Highly Luminescent Copper Iodide Cluster Based Inks with
Photoluminescence Quantum Efficiency Exceeding 98%
Jing-Jing Wang, Chen Chen, Wei-Guo Chen, Ji-Song Yao, Jun-Nan Yang, Kun-Hua Wang,
Yi-Chen Yin, Ming-Ming Yao, Li-Zhe Feng, Cheng Ma, Feng-Jia Fan, and Hong-Bin Yao
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b12908 • Publication Date (Web): 11 Feb 2020
Downloaded from pubs.acs.org on February 11, 2020
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 6
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
Highly Luminescent Copper Iodide Cluster Based Inks with
Photoluminescence Quantum Efficiency Exceeding 98%
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Jing-Jing Wang1,2,†, Chen Chen1,2,†, Wei-Guo Chen , Ji-Song Yao , Jun-Nan Yang , Kun-Hua Wang , Yi-Chen Yin , Ming-
4,5
1,2
1,2
1,2
1,2
Ming Yao , Li-Zhe Feng , Cheng Ma, Feng-Jia Fan4,5,6 and Hong-Bin Yao*1,2
1,2
1,2
1,3
1Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science
and Technology of China, Hefei, Anhui 230026, China
2
Department of Applied Chemistry, Hefei Science Center of Chinese Academy of Sciences, University of Science and Technology
of China, Hefei, Anhui 230026, China
3
Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, China
Department of Physics, Hefei Science Center of Chinese Academy of Sciences, University of Science and Technology of
4
China, Hefei, Anhui 230026, China
5
CAS Key Laboratory of Microscale Magnetic Resonance, University of Science and Technology of China, Hefei,
Anhui 230026, China
6
Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China,
Hefei, Anhui 230026, China
Supporting Information Placeholder
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
those based on carbon dots with excellent biocompatibility suffer
from the photo bleaching behavior and low photoluminescence
quantum efficiency (PLQE), which severely limit their practical
applications.2-3, 8 Moreover, tedious synthesis processes of most
luminescent components hinder their practical applications and lead
to some difficulties in large scale fabrication. These bring about a
necessity to develop a cost effective, environmental friendly, easily
scalable and strong emissive luminescent ink.
Copper-iodide (Cu-I) cluster based organic-inorganic hybrids
have been extensively explored recently as alternative phosphors in
virtue of their earth abundance, low cytotoxicity, structural
diversity and high luminescent efficiency.10-12 Nevertheless, the
fabrication of luminescent inks based on Cu-I hybrids has to face
the challenges ascribed to their poor solubility and dispersibility in
solvents. To address this, our group have adopted a microemulsion
strategy to produce the Cu-I based hybrid cluster inks with an
aggregation-induced emission process, yet the synthetic routes
required using toxic organic solvents and the obtained inks behaved
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
ABSTRACT: Highly luminescent inks are desirable for various
applications such as decorative coating, art painting, anti-
counterfeiting, to name a few. However, present inks display low
photoluminescent efficiency requiring a strong excitation light to
make them shining. Here, we report a highly luminescent ink based
on the copper-iodide/1-Propyl-1,4-diazabicyclo[2.2.2]octan-1-ium
9
(Cu
98%. Under the interaction between Cu
and polyvinylpyrrolidone (PVP), the highly luminescent Cu
ted) /PVP ink can be facilely prepared via the one-pot solution
synthesis. The obtained ink exhibits strong green light emission that
originates from the efficient phosphorescence of Cu (pr-ted)
4
I
6
(pr-ted)
2
) hybrid cluster with a quantum efficiency exceeding
(pr-ted) hybrid cluster
(pr-
4
I
6
2
4 6
I
1
1
1
1
1
1
1
2
4
I
6
2
nanocrystals. Attractively, the ink displays high conversion
efficiency for the ultraviolet light to bright green light emission due
to its wide Stokes-shift, implying great potentials for anti-
counterfeiting and luminescent solar concentrator coating.
43 a little poor dispersibility and thermal stability.13 Very recently, a
44 new type Cu-I cluster based hybrid with special all-in-one structure,
45 containing ionic and covalent bonds between the inorganic core and
46 organic ligands, has been reported.14-15 This new kind of Cu-I based
47 hybrid is composed of isolated clusters possessing high structural
48 stability and efficient phosphorescence due to the strong spin-
49 orbital coupling in the cluster, which imply a tremendous potential
50 for the fabrication of stable and highly luminescent inks.
17
18
19
20
21
22
23
24
Environmental-friendly and highly luminescent inks are in
diverse demands for indispensable applications such as functional
coatings, anti-counterfeiting printings, art paintings and so forth.
Currently, various luminescent inks have been prepared by using
carbon dots,1-3 rare-earth-doped compounds,4-5 inorganic
semiconductor complexes,6 and organic dyes.7 However, the
luminescent inks based on rare-earth elements and heavy metals are
subjected to high cost and potential environmental issues, while
1
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 6
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
Herein, we use the all-in-one structured Cu
4
I
6
(pr-ted)
2
hybrid
44 micelles played a crucial role during this process on stabilizing Cu-I
clusters as basic building blocks to prepare highly luminescent ink
via an environmental-friendly and facile solution synthetic route.
We introduce a highly affinity polymer polyvinylpyrrolidone (PVP)
to stabilize and disperse the anionic Cu-I inorganic units,
facilitating the aggregation with cationic 1-propyl-1,4-
diazabicyclo[2.2.2]octan-1-ium (pr-ted) ligands via both
45 units because the control experiment showed the precipitating of
46 CuI when adding to the ethanol solution without PVP (Figure S2).
47 Upon consequent addition of the pr-ted ligands, the clear solution
48 immediately became a white-yellow suspensoid, emitting strong
49 green light under the irradiation of ultraviolet light (Figure 1d).
50
coordinative and electrostatic interaction to form the Cu
nanocrystals in the PVP micelles. The obtained inks exhibit
4 6 2
I (pr-ted)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
10 excellent dispersibility in ethanol and water, achieving a PLQE up
11 to nearly 100%. The high luminescence of the obtained inks is
12 originated from the phosphorescent emission from the structurally
13 stable Cu I (pr-ted) hybrid cluster and its wide Stokes-shift is
4 6 2
14 essential for the anti-counterfeiting picture and luminescent solar
15 concentrator coating.
5
1
5
5
5
5
2
3
4
5
Figure 2. (a) PXRD pattern of as-synthesized nanoparticles (red) and
simulated XRD pattern from Cu (pr-ted) single crystal structure
(black). (b) FT-IR spectra of as-synthesized Cu (pr-ted) powder
(black), Cu (pr-ted) /PVP nanoparticles (red) and pure PVP (blue). (c)
(pr-ted) powder (black), Cu (pr-ted) /PVP
nanoparticle (red) and pure PVP (blue), respectively. (d) TEM image of
Cu (pr-ted) /PVP single nanoparticle synthesized by using PVP K88-
96 with the concentration of 0.01g mL . (e) HRTEM image of the
Cu (pr-ted) /PVP nanoparticle with an inset SAED pattern. (f) SEM
(pr-ted) /PVP nanoparticles synthesized by using PVP
62 K88-96 with the concentration of 0.01 g mL .
4
I
6
2
4
I
6
2
4
I
6
2
56 TG curves of Cu
4
I
6
2
4
I
6
2
5
5
5
6
7
8
9
0
4
I
6
2
-1
4
I
6
2
61 image of Cu
4
I
6
2
-
1
6
6
6
3
4
5
To investigate the influence of PVP on the dispersion stability of
the obtained inks, we separately regulated the type and the amount
of PVP in the solution synthesis system and the optimized condition
1
6
17 Figure 1. (a) Schematic illustration of PVP stabilized coordination
1
1
2
2
8
9
0
1
process of copper-iodide inorganic units and cationic ligands for the
formation of luminescent nanocrystals. (b) A colorless clear solution
formed by dissolving PVP in the ethanol. (c) A pale yellow clear
solution of saturated KI solution of CuI added into the PVP/ethanol
-1
66 for the preparation of luminescent inks is using 0.01 g mL of PVP
67 K88-96 (Figure S3). The phase of the obtained nanoparticles was
6
6
7
8
9
0
revealed by the powder X-ray diffraction (PXRD) pattern (Figure
2a), which is consistent with the simulated XRD pattern, confirming
the formation of crystalline Cu I (pr-ted) . The Fourier-transform
4 6 2
22 solution. (d) A white colloidal nanoparticle suspension formed
23 immediately after the addition of the pr-ted ligands to the Cu-I precursor
4
5
2
2
solution. Inset: photograph of the obtained colloidal nanoparticle
suspension under the irradiation of ultraviolet light (365 nm).
71 infrared spectroscopy (FT-IR) showed that the bands appeared at
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
1660 cm-1 and 1290 cm-1 in the obtained nanoparticles
corresponding to the C=O and C–N vibration modes of PVP,
respectively, indicating the existence of PVP (Figure 2b), and the
positive shift of C=O stretching band (Figure S4) indicates that
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
As shown in Figure 1a, in our developed synthetic system, the
long chain PVP entangles with each other into a micelle structure
to confine the Cu-I units inside to form a stable dispersion due to
steric hindrance. Once the pr-ted cationic ligands are added into the
precursor solution, these ligands quickly diffuse into the PVP chain
section. Owing to both the electrostatic attraction and coordinative
interaction, pr-ted ligands react with the Cu-I inorganic units to
Cu
PVP.16-17 The thermogravimetric (TG) curves of Cu
ted) /PVP nanoparticle, Cu (pr-ted) powder, and pure PVP
manifest that the weight loss of the composite nanoparticles was
obviously larger than that of pure Cu (pr-ted) (Figure 2c), further
4
I
6
(pr-ted)
2
nanocrystals coordinate with the nitrogen atoms in
4 6
I
(pr-
2
4
I
6
2
form the Cu
generated crystals are further confined inside of the PVP micelles,
forming the Cu (pr-ted) /PVP composite nanoparticles. Our
proposed strategy can be used for a large-scale preparation of
strongly luminescent and stable Cu (pr-ted) cluster based ink
4 6 2
I (pr-ted) hybrid crystals (Figure S1). Moreover, the
4
I
6
2
indicating that PVP still presented in the formed nanoparticles even
after the centrifugation-washing purification processes. These
results demonstrated that PVP not only played an important role in
stabilizing the dispersion of the ink, but also participated in the
4
I
6
2
4
I
6
2
(Video S1). As shown in Figure 1b, we used a one liter reaction
vessel with a certain amount of PVP powder dissolving in the
ethanol. Simultaneously, the CuI powder was dissolved in the
saturated KI aqueous solution and then slowly added to the above
PVP/ethanol solution under mechanical stirring to yield a pale
yellow transparent CuI/PVP mixed solution (Figure 1c). The PVP
4 6 2
formation of Cu I (pr-ted) /PVP composite nanoparticles.
Transmission electron microscopy (TEM) image (Figure 2d) also
shows that the composite nanoparticle is consisted of amorphous
PVP matrix, in which many small crystalline sub-particles (~20 nm)
are dispersed (Figure S5). High resolution TEM image (Figure 2e)
further shows that the lattice fringe spacing of the crystalline sub-
2
ACS Paragon Plus Environment

Page 3 of 6
1
Journal of the American Chemical Society
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
particle is 0.42 nm, corresponding to the interplanar spacing of
(222) plane of Cu (pr-ted) crystal. Moreover, the electron
diffraction rings of (111) and (222) planes from selected area
electron diffraction (SAED) pattern (inset in Figure 2e) manifest the
4 6 2
polycrystalline characteristic of Cu I (pr-ted) in the composite
nanoparticles. Besides, scanning electron microscopy (SEM) image
(Figure 2f) shows that the nanoparticles are interconnected with
each other, also implying that the PVP acted as the matrix to load
38 fabricated
Cu
4
I
6
(pr-ted)
2
/PVP
nanoparticles
exhibited
4
I
6
2
39 thermochromic behavior (Figure 3c), which is decreasing
40 temperature resulting in small blue shift in the emission peak
41 accompanied by width narrowing. This is a typical characteristic of
42 the reduced structural torsion and increased localization of the
43 excited state on the molecular structure of Cu
44 Therefore, the bright emission of Cu (pr-ted)
45 from the Cu (pr-ted) cluster, the mechanism of which can be
4
I
6
(pr-ted)
2
cluster.14
4
I
6
2
/PVP ink comes
4
I
6
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
the discrete crystalline Cu
4
I
6
(pr-ted)
2
sub-particles forming the
46 described as phosphorescence arising from the radiative
47 recombination of electrons passing through intersystem crossing
10 Cu
4
I
6
(pr-ted) /PVP composite nanoparticles.
2
48 (ISC) process in the lowest excited triplet state (T
49 ground state (S ) (Figure 3d). The large optical band difference
50 between S state and T state (ΔE) also results in the wide Stokes-
51 shift of the obtained Cu (pr-ted)
/PVP ink.18 The wide Stokes-
52 shift of the ink indicates its potential as an ultraviolet shielding
53 coating on the substrate (Figure 3e and f). In contrast to the normal
54 glass of a transmittance over 70% in ultraviolet region, the glass
1
) with holes in
0
1
1
4
I
6
2
4 6 2
55 substrate coated by Cu I (pr-ted) /PVP nanoparticles exhibited an
56 excellent ultraviolet shielding effect with an average ultraviolet
57 light transmittance of less than 20%. Moreover, the photographs of
58 the substrates under ultraviolet light (365 nm) irradiation (insets in
59 Figure 3e and f) show the clear shadow under the Cu
60 ted) /PVP nanoparticle coated substrate in comparison to very light
61 shadow under normal glass substrate without any coatings.
4 6
I (pr-
2
11
1
1
2
3
Figure 3. (a) UV-vis absorption spectrum and PL spectrum (λex = 365
nm) of the obtained ink. (b-c) PL decay profiles and emission spectra
14 of Cu
4
I
6
(pr-ted)
nm), respectively. (d) Energy diagrams of phosphorescence emission
process of Cu (pr-ted) /PVP nanoparticles. (e-f) Light transmittance
spectra of normal glass substrate and the glass substrate coated with
Cu (pr-ted) nanoparticle film, respectively. Inset: corresponding
2
/PVP nanoparticles at various temperatures (λex = 365
15
16
17
18
4
I
6
2
4
I
6
2
19 photographs of ultraviolet light (365 nm) irradiation on the white printer
20 paper through the substrate.
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
4 6 2
The optical properties of the obtained stable Cu I (pr-ted) /PVP
inks (Figure S6) were unraveled by a series of spectroscopy
analysis. As shown in Figure 3a, the UV-vis absorption spectrum
indicates that Cu
absorption to the light with the wavelength lower than 400 nm due
to the intrinsic light absorption of Cu (pr-ted) cluster and PVP.
The PL spectrum displays a strong emission peak at 526 nm with a
high PLQE of 98.6 %. More interestingly, the ink has a wide
Stokes-shift of 113.8 nm, indicating a large energy level difference
between the absorption excitation state and PL emission state. The
4 6 2
I (pr-ted) /PVP ink behaves very strong
4
I
6
2
6
2
4 6 2
PL lifetime of Cu I (pr-ted) /PVP ink recorded at different
temperatures shows little dependence on the temperate variation
(Figure 3b) and the PL lifetime decay curves are good fit with a
single (first-order) exponential decay function (Table S1), with an
average PL lifetime decay constant of ~ 25 μs, which is different
from the highly temperature dependent PL decay lifetime of
4 6 2
63 Figure 4. (a) A picture painted by the Cu I (pr-ted) /PVP ink under
64 natural light and 365 nm ultraviolet light, respectively. (b) A large areal
6
5
6
highly luminescent Cu
substrate by a doctor-blade coating process. (c) Comparison of PL
(pr-
4 6 2
I (pr-ted) /PVP film fabricated on the glass
6
67 intensities as a function of propagation lengths in the Cu
ted) /PVP film and CsPbBr nanocrystal film, respectively.
4 6
I
6
8
2
3
thermally activated delayed fluorescence.14-15 Moreover, the as-
3
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 6
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
The unique optical properties of Cu
4
I
6
(pr-ted)
2
/PVP ink with
51 ACKNOWLEDGEMENT
high PLQE and wide Stokes-shift imply its great potential for
various applications. We first used it to draw an anti-counterfeiting
picture. As shown in Figure 4a, a bamboo picture drew by the
5
5
5
5
5
5
5
5
6
6
6
2
3
4
5
6
7
8
9
0
1
2
This work is supported by the National Natural Science Foundation
of China (Grants 51571184, 21875236, 81788101, 11761131011),
the Fundamental Research Funds for the Central Universities
(Grant WK2060190085), the joint Funds from Hefei National
Synchrotron Radiation Laboratory (Grant KY2060000111), the
National Key R&D Program of China (Grant No.
2018YFA0306600), the CAS (Grants No. GJJSTD20170001 and
No. QYZDY-SSW-SLH004) and Anhui Initiative in Quantum
Information Technologies (Grant No. AHY050000). This work was
partially carried out at the USTC Center for Micro and Nanoscale
Research and Fabrication.
Cu
becomes shinning when exposed to ultraviolet light (365 nm).
Furthermore, the Cu (pr-ted) /PVP ink is a good candidate for
4 6 2
I (pr-ted) /PVP ink was nearly colorless under natural light but
4
I
6
2
luminescent solar concentrator (LSC) coating in photovoltaic
devices due to its wide Stokes-shift (Figure S7).19-21 To demonstrate
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4 6 2
10 the application of Cu I (pr-ted) /PVP ink for LSC coating, we
11 introduced a high concentration of PVP K30 as polymer matrix and
12 optimized the conditions to fabricate highly transparent films
13 (Figure S8-S11). As shown in Figure 4b, a uniform and strongly
14 luminescent film on a large rectangular quartz substrate (9 cm × 4.5
15 cm) can be fabricated via a facile doctor-blade coating technique.
6
6
3 REFERENCES
4
(1) Liu, Y. B.; Zhou, L.; Li, Y. N.; Deng, R. P.; Zhang, H. J., Highly
16 The Cu
4
I
6
(pr-ted)
2
/PVP composite film and CsPbBr
3
nanocrystal
65 fluorescent nitrogen-doped carbon dots with excellent thermal and photo
6
6
6
6
6
7
8
9
stability applied as invisible ink for loading important information and anti-
counterfeiting. Nanoscale 2017, 9 (2), 491-496.
(2) Qu, S. N.; Wang, X. Y.; Lu, Q. P.; Liu, X. Y.; Wang, L. J., A
Biocompatible Fluorescent Ink Based on Water-Soluble Luminescent
17 film with same size (Figure S12) were prepared to test their LSC
18 behavior (Figure S13 and S14). The PL intensity as a function of
19 propagation length of the light conduction in the film was recorded
20 (Figure 4c). As the detection distance increased from 0.5 to 5.5 cm,
21 the Cu
22 due to the less self-absorption of Cu
23 induced by the wide Stokes-shift and the better waveguide property
24 (Figure S15). Moreover, the Cu (pr-ted) /PVP film shows good
70 Carbon Nanodots. Angew. Chem. Int. Edit. 2012, 51 (49), 12215-12218.
7
7
7
1
2
3
(3) Atchudan, R.; Edison, T. N. J. I.; Aseer, K. R.; Perumal, S.; Karthik,
N.; Lee, Y. R., Highly fluorescent nitrogen-doped carbon dots derived from
Phyllanthus acidus utilized as a fluorescent probe for label-free selective
4
I
6
(pr-ted)
2
/PVP film displayed slower PL intensity decay
4
I
6
(pr-ted) /PVP nanoparticles
2
3
+
74 detection of Fe ions, live cell imaging and fluorescent ink. Biosens.
7
7
7
5
6
7
Bioelectron. 2018, 99, 303-311.
4
I
6
2
(4) Gangwar, A. K.; Nagpal, K.; Kumar, P.; Singh, N.; Gupta, B. K., New
insight into printable europium doped yttrium borate luminescent pigment
25 stability under the continuous irradiation of the simulated sunlight
26 (Figure S16), implying its potential application for LSC.
27
78 for security ink application. J. Appl. Phys. 2019, 125 (7), 074903.
7
8
8
9
0
1
(5) Xie, S. W.; Gong, G.; Song, Y.; Tan, H. H.; Zhang, C. F.; Li, N.;
Zhang, Y. X.; Xu, L. J.; Xu, J. X.; Zheng, J., Design of novel lanthanide-
doped core-shell nanocrystals with dual up-conversion and down-
In summary, we have prepared highly luminescent Cu
4 6
I (pr-
28 ted)
2
/PVP ink in a large scale via an environmental-friendly and
29 facile route by taking advantages of good crystalline of ionic Cu-I
30 hybrid clusters and PVP micelle confinement. The obtained
31 Cu I (pr-ted) /PVP composite nanoparticles can be well dispersed
4 6 2
32 in ethanol and water, showing a high PLQE exceeding 98% and a
33 wide Stokes-shift due to the high efficient phosphorescent emission
34 of Cu
35 ted) /PVP ink to draw an anti-counterfeiting picture and fabricate a
36 uniform Cu (pr-ted) /PVP film to prove an essential application
82 conversion luminescence for anti-counterfeiting printing. Dalton Trans.
83 2019, 48 (20), 6971-6983.
8
8
8
4
5
6
(6) Xu, L. M.; Chen, J. W.; Song, J. Z.; Li, J. H.; Xue, J.; Dong, Y. H.;
Cai, B.; Shan, Q. S.; Han, B. N.; Zeng, H. B., Double-Protected All-
Inorganic Perovskite Nanocrystals by Crystalline Matrix and Silica for
87 Triple-Modal Anti-Counterfeiting Codes. Acs Appl. Mater. Interfaces 2017,
8
8
9
8
9
0
9 (31), 26556-26564.
4 6 2 4 6
I (pr-ted) hybrid cluster. We have used the Cu I (pr-
(7) Liu, J. B.; Zhuang, Y. X.; Wang, L.; Zhou, T. L.; Hirosaki, N.; Xie,
R. J., Achieving Multicolor Long-Lived Luminescence in Dye-
2
4
I
6
2
91 Encapsulated Metal-Organic Frameworks and Its Application to
9
9
9
2
3
4
Anticounterfeiting Stamps. Acs Appl. Mater. Interfaces 2018, 10 (2), 1802-
1809.
(8) Shi, L. H.; Li, Y. Y.; Li, X. F.; Wen, X. P.; Zhang, G. M.; Yang, J.;
37 prospect for the LSC device.
38 ASSOCIATED CONTENT
95 Dong, C.; Shuang, S. M., Facile and eco-friendly synthesis of green
fluorescent carbon nanodots for applications in bioimaging, patterning and
97 staining. Nanoscale 2015, 7 (16), 7394-7401.
(9) Liu, F.; Nattestad, A.; Naficy, S.; Han, R.; Cosillas, G.; Angeloski,
9
6
3
9
Supporting Information
9
8
4
4
4
4
0
1
2
3
Experimental details, crystal structure, photograghs, schematics, PL
spectra, SEM mapping, including Figures S1-S9 and Table S1. This
material is avail-able free of charge via the Internet at
http://pubs.acs.org.
99 A.; Sun, X. D.; Huang, Z. G., Fluorescent Carbon- and Oxygen-Doped
100 Hexagonal Boron Nitride Powders as Printing Ink for Anticounterfeit
101 Applications. Adv. Opt. Mater. 2019, 1901380.
1
1
02 (10) Fang, Y.; Liu, W.; Teat, S. J.; Dey, G.; Shen, Z.; An, L.; Yu, D.;
03 Wang, L.; O'Carroll, D. M.; Li, J., A Systematic Approach to Achieving
104 High Performance Hybrid Lighting Phosphors with Excellent Thermal- and
4
4
AUTHOR INFORMATION
105 Photostability. Adv. Funct. Mater. 2017, 27 (3), 1603444.
1
06 (11) Liu, W.; Fang, Y.; Wei, G. Z.; Teat, S. J.; Xiong, K.; Hu, Z.; Lustig,
4
4
5
6
Corresponding Author
107 W. P.; Li, J., A Family of Highly Efficient CuI-Based Lighting Phosphors
108 Prepared by a Systematic, Bottom-up Synthetic Approach. J. Am. Chem.
*yhb@ustc.edu.cn
1
1
1
09 Soc. 2015, 137 (29), 9400-8.
10 (12) Zhang, X.; Liu, W.; Wei, G. Z.; Banerjee, D.; Hu, Z.; Li, J.,
11 Systematic Approach in Designing Rare-Earth-Free Hybrid Semiconductor
47 Author Contributions
112 Phosphors for General Lighting Applications. J. Am. Chem. Soc. 2014, 136
13 (40), 14230-6.
114 (13) Chen, C.; Li, R. H.; Zhu, B. S.; Wang, K. H.; Yao, J. S.; Yin, Y. C.;
15 Yao, M. M.; Yao, H. B.; Yu, S. H., Highly Luminescent Inks: Aggregation-
4
4
8
9
†These authors contributed equally to this work.
1
Notes
1
50 The authors declare no competing financial interest.
4
ACS Paragon Plus Environment

Page 5 of 6
1
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
0
1
2
Induced Emission of Copper-Iodine Hybrid Clusters. Angew. Chem. Int. Ed.
17 (18) Leitl, M. J.; Krylova, V. A.; Djurovich, P. I.; Thompson, M. E.;
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2018, 57 (24), 7106-7110.
18 Yersin, H., Phosphorescence versus Thermally Activated Delayed
19 Fluorescence. Controlling Singlet-Triplet Splitting in Brightly Emitting and
20 Sublimable Cu(I) Compounds. J. Am. Chem. Soc. 2014, 136 (45), 16032-
21 16038.
22 (19) Meinardi, F.; Bruni, F.; Brovelli, S., Luminescent solar concentrators
23 for building-integrated photovoltaics. Nat. Rev. Mater. 2017, 2 (12).
24 (20) Debije, M. G.; Verbunt, P. P. C., Thirty Years of Luminescent Solar
25 Concentrator Research: Solar Energy for the Built Environment. Adv.
26 Energy Mater. 2012, 2 (1), 12-35.
27 (21) Van Sark, W. G. J. H. M.; Barnham, K. W. J.; Slooff, L. H.; Chatten,
28 A. J.; Buchtemann, A.; Meyer, A.; McCormack, S. J.; Koole, R.; Farrell, D.
29 J.; Bose, R.; Bende, E. E.; Burgers, A. R.; Budel, T.; Quilitz, J.; Kennedy,
30 M.; Meyer, T.; Donega, C. D. M.; Meijerink, A.; Vanmaekelbergh, D.,
31 Luminescent solar concentrators - a review of recent results. Opt. Express
32 2008, 16 (26), 21773-21792.
(14) Liu, W.; Zhu, K.; Teat, S. J.; Dey, G.; Shen, Z.; Wang, L.; O'Carroll,
D. M.; Li, J., All-in-One: Achieving Robust, Strongly Luminescent and
Highly Dispersible Hybrid Materials by Combining Ionic and Coordinate
Bonds in Molecular Crystals. J. Am. Chem. Soc. 2017, 139 (27), 9281-9290.
(15) Liu, W.; Fang, Y.; Li, J., Copper Iodide Based Hybrid Phosphors for
Energy-Efficient General Lighting Technologies. Adv. Funct. Mater. 2018,
28 (8), 1705593.
(16) Koczkur, K. M.; Mourdikoudis, S.; Polavarapu, L.; Skrabalak, S. E.,
Polyvinylpyrrolidone (PVP) in nanoparticle synthesis. Dalton Trans. 2015,
44 (41), 17883-17905.
1
1
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
13 (17) Xu, L.; Wang, G. L.; Zheng, X. S.; Pan, H. B.; Zhu, J. F.; Li, Z. Y.;
1
1
1
4
5
6
Yu, S. H., Competitive Adsorption between a Polymer and Its Monomeric
Analog Enables Precise Modulation of Nanowire Synthesis. Chem 2018, 4
(10), 2451-2462.
33
5
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 6
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Artwork for TOC
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
ACS Paragon Plus Environment