Incorporation of an Emissive Cu4I4Core into Cross-Linked Networks: An Effective Strategy for Luminescent Organic-Inorganic Hybrid Coatings

Article abstract of DOI:10.1021/acs.inorgchem.1c00909

Here, an effective strategy for the preparation of luminescent organic-inorganic hybrid coatings (OIHCs) by the incorporation of an emissive Cu4I4 core into cross-linked coating networks through coordination bonds is reported. The luminescent coatings obt

Full text of DOI:10.1021/acs.inorgchem.1c00909

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Incorporation of an Emissive Cu4I4 Core into Cross-Linked Networks:
An Effective Strategy for Luminescent Organic−Inorganic Hybrid
Coatings
Hua Tong, Haibo Li, Haojun Li, Cidanpuchi, Fuchen Wang, and Wei Liu*
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ABSTRACT: Here, an effective strategy for the preparation of
luminescent organic−inorganic hybrid coatings (OIHCs) by the
incorporation of an emissive Cu4I4 core into cross-linked coating
networks through coordination bonds is reported. The luminescent
coatings obtained show potential application in a variety of areas,
and such a synthetic strategy of the incorporation of an emissive
inorganic core into extended networks has proven to be an efficient method for the synthesis of luminescent OIHCs.
rganic−inorganic hybrid materials have been known for
coatings, which are able to respond to changes in the
Odecades, and these hybrid compounds exhibit unique environment for the applications in monitoring and early
warning of corrosion.37−39 They can also be used as decorative
coatings, anticounterfeiting printings, art paintings, etc.40 At
present, the luminescent OIHCs are mainly prepared by
adding luminescent materials, such as phosphors, into the
hybrid coatings to achieve the light-emitting performance.41,42
Such a physical mixing of the multicomponents may lead to
the problem of nonuniform dispersion of the luminophores
and the precipitation of luminescent particles. In addition, the
phosphors used are generally rare-earth-based and may bring
environmental issues. Therefore, developing new and facile
strategies for better-performing luminescent OIHCs is of great
significance.
properties.1−4 The combination of inorganic species and
organic ligands leverages the advantages of both components
and would lead to new and novel properties.5,6 Scientists can
easily alter the structure of hybrid compounds to investigate
their structure−property relationships.7−10 These hybrid
structures exhibit potential applications in a variety of areas,
including solid-state lighting, solar cells, functional coatings,
etc.9,11−17 Better-performance functional hybrid structures are
in high demand in these areas.
Corrosion has always been a worldwide problem because it
attacks our environment and may have serious consequen-
ces.18−21 Protective coatings are the most direct and effective
way to protect metallic materials from corrosion.22−25
Organic−inorganic hybrid coatings (OIHCs) are a very
important application of organic−inorganic hybrid materials.
The OIHCs display various advantages compared to pure
organic or inorganic coatings, such as low volatile organic
content, good corrosion protection and adhesion properties on
metallic substrates, etc. One of the commonly used methods to
synthesize OIHCs is the sol−gel method, and tetraethoxysilane
(TEOS) is typically used as the precursor that undergoes
hydrolysis and condensation reactions, forming a self-
assembled network.26−29 The formed coatings prevent contact
between the corrosive species and metallic substrates, and their
protective properties can be systematically tuned by adjusting
the reaction conditions and the composition of the coating
materials.30−32
Inspired by the early studies, we report an effective strategy
for the preparation of luminescent OIHCs by the incorpo-
ration of an emissive Cu4I4 core into cross-linked coating
networks through coordination bonds.43−48 Phosphines are
common organic ligands for the synthesis of copper iodide
based hybrid structures. One of the most used members,
triphenylphosphine (tpp) has been frequently used for the
construction of Cu2I2 or Cu4I4 discrete cluster-based
compounds because of the steric hindrance of the tpp
molecules.49 Here, a tpp derivative, P-containing silane
coupling agent 2-(diphenylphosphino)ethyltriethoxysilane
(dpes) with a structure similar to that of tpp, has been
selected as the precursor for the preparation of OIHCs (Figure
S1). The P atoms on dpes would coordinate to Cu, forming a
Received: March 29, 2021
In order to achieve better performance and more
functionalities, the development of multifunctional coatings
with luminescence, self-healing ability, high-thermal stability,
and mechanical resistance have been very hot topics.21,33−36
Among them, luminescent coatings represent an important
class of functional coatings, and they can be used as intelligent
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Cu4I4 core when reacted with CuI, resulting in a new Cu4I4-
cluster-containing silane coupling agent (Cu4I4-dpes; Figure
1a). Cu4I4-dpes could be further hydrolyzed and condensed
of the van der Waals radii 2.8 Å) in the Cu4I4 core leads to a
series of unique optical properties. Thermochromic and
mechanochromic luminescence has been reported for Cu4I4-
based clusters.53,54 Cu4I4-based extended structures are
typically more stable compared to molecular clusters of this
type.44,46
The preparation of Cu4I4-dpes was conducted in reaction
vials at room temperature. dpes was added into a suspension
CuI in dichloromethane. The reaction mixture was stirred for a
few hours at room temperature and filtered. Interestingly, the
reaction mixture became almost transparent after the reaction,
indicating that the insoluble CuI in the reaction mixture has
reacted with dpes. A high-viscosity transparent oil Cu4I4-dpes
was obtained after the slow evaporation of dichloromethane,
emitting a strong yellow emission under UV-light irradiation.
Because all of the reactants are not luminescent, the yellow
emission from the oil indicates the formation of an emissive
Cu4I4 core in the extended structures. Because single crystals of
this compound could not be obtained, we used another
phosphine ligand, tris(4-fluorophenyl)phosphane (F-tpp), as
the organic ligand instead of dpes for the reaction with CuI
and obtained single crystals (Figure S2). The single-crystal X-
ray diffraction results show that it is a Cu4I4 cubane tetramer-
based molecular cluster, 0D-Cu4I4(F-tpp)4 (Figure 1b). The
detailed crystallographic data have been summarized in Table
S1. The power X-ray diffraction (PXRD) patterns of 0D-
Cu4I4(F-tpp)4 are shown in Figure S3. The resemblance of the
structures of the organic ligands and the reaction conditions
indicate that it is highly possible that the transparent oil
Figure 1. (a) Structural plot of synthesized Cu4I4-dpes. (b) Structure
plot of 0D-Cu4I4(F-tpp)4. (c) Illustration of the cross-linked network
structure of compound 1.
1
formed is a Cu4I4-based structure. The H NMR spectrum of
with other coupling reagents to form cross-linked OIHCs
(Figure 1c). The proposed strategy is suitable for the large-
scale preparation of strongly luminescent and stable Cu4I4-
based hybrid coating materials. dpes not only plays an
important role in the formation of a Cu4I4 core but also as a
coupling reagent, forming cross-linked coating networks.
The Cu4I4 emissive inorganic core has been well-studied for
its phosphorescence originating from the strong Cu−Cu
interaction.44,50−52 Cu4I4 cubane tetramer-based structures
have the general formula Cu4I4(L)n and have been intensively
studied.44,45 The shorter Cu−Cu distance (less than the sum
Cu4I4-dpes is shown in Figure S4. OIHCs were further
prepared by a sol−gel method with Cu4I4-dpes and TEOS
under acidic conditions. The transparent viscous liquid was
obtained by evaporation of the solvent. The liquid was
uniformly coated onto quartz substrates by a spin-coating
technique. A uniform coating film was formed on a quartz
substrate with a thickness of 3 μm (Figure S5). The OIHC
materials have been completely dried as a white powder
(compound 1) for structural and optical characterizations.
X-ray photoelectron spectroscopy (XPS) was employed to
confirm the composition of the OIHC material. As shown in
Figure 2. (a) XPS spectra of the (a) survey, (b) C 1s, (c) O 1s, (d) Si 2p, (e) P 2p, (f) Cu 2p, and (g) I 3d of the OIHC material.
B
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Figure 2a, only the C, O, Si, P, Cu, and I elements are detected
in the XPS survey, indicating the high purity of the OIHC
coating. In the C 1s XPS spectrum (Figure 2b), the main peak
at 284.8 eV is consistent with the dominant phenyl
contribution.43 The minor peak at around 286 eV should
have originated from the adventitious atmospheric organic
pollutants. The O 1s and Si 2p spectra (Figure 2c,d) possess
highly symmetric peaks at 532.9 and 103.6 eV, respectively,
indicating a uniform Si−O−Si major constitution and
coinciding with the SiO2 sol−gel configuration with silicon-
(IV) species.43 The P 2p signal at 131.1 eV is in agreement
with the reported P atom corresponding to the phosphine
ligand coordinated to Cu atoms (Figure 2e).55 As for the Cu
and I elements, both Cu 2p3/2 at 933.0 eV and I 3d5/2 at 619.4
eV are consistent with the Cu4I4 XPS data from the literature
(933.00 and 619.72 eV, respectively), demonstrating the
existence of Cu4I4 (Figure 2f,g).43 Notably, the atomic
percentages of P, Cu, and I are 0.3%, 0.25%, and 0.2%,
respectively (Table S2), indicating that the P/Cu/I ratio is
approximatively 1/1/1.
coatings on the quartz substrates are transparent (inset of
Figure 3b). Because the Cu4I4 core is incorporated in the
hybrid coatings, the optical properties of 1 are similar
compared to that of other Cu4I4-based hybrid structures.
Density of states (DOS) calculations of 0D-Cu4I4(F-tpp)4
(Figure 3d) demonstrate similarities and differences in the
atomic state distributions compared to other Cu4I4-based
hybrid structures, indicating that the optical properties of the
Cu4I4-based hybrid coatings can be systematically tuned by
changing either the inorganic species or organic ligands.44,45,45
The photoluminescence (PL) spectrum of compound 1 is
shown in Figure 4a. The yellow emission peak at 580 nm has a
full width at half-maximum (fwhm) of around 110 nm. A 40
nm blue shift was observed compared to its precursor Cu4I4-
dpes (Figure S6). Compound 1 shows a large Stokes shift of
∼325 nm, exhibiting a large energy-level difference between
the absorption excitation state and PL emission state.
Compared to the emission of 0D-Cu4I4(F-tpp)4, compound
1 shows a red shift of around 30 nm (Figure S7). The internal
quantum yield of 1 was measured to be 8.5% under 300 nm
excitation, which is relatively lower compared to those of other
Cu4I4-based compounds.44 The Commission Internationale de
l’Eclairage (CIE) chromaticity coordinates (Figure 4b) for the
emission were calculated to be (0.49, 0.50), indicating that the
emission of compound 1 is orange-yellow light.
In the OIHC material obtained, there are two types of
inorganic species: CuI and silica. The two types of inorganic
cores are interconnected by the organic species, forming a
cross-linked network (Figure 1c). PXRD analyses have been
carried out, and the results show that the as-made network is
totally amorphous structure (Figure 3a). No peak for CuI has
As shown in previous studies for Cu4I4-based clusters,
thermochromic luminescence of compound 1 is revealed by
immersion of 1 in liquid nitrogen.54 Under the same UV
excitation, the orange-yellow emission becomes a sharp-yellow
emission (inset of Figure S8). The emission spectrum of
compound 1 at 77 K has been collected (Figure S8), which
shows that the emission intensity increases and the emission
band becomes narrower at lowered temperatures. Also, blue
shifts in the emission energies have been observed as the
temperature is decreased. About a 20 nm blue shift in its
emission spectrum was observed by lowering the temperature
from room temperature to 77 K. This can be explained by the
reduced structural torsion and increased localization of the
excited state on the Cu4I4L4 cluster.56 Figure S9 displays the
luminescence decay of 1 at room temperature, and it shows
that compound 1 has a long lifetime of approximately 2.35 μs
by monoexponential fitting. This is in accordance with the
lifetime values of other luminescent Cu4I4-based organic−
inorganic hybrid materials.45
The sol−gel coating materials are luminescent under UV
excitation (inset of Figure 4a) and can be coated onto the
various kinds of substrates by a spin-coating technique. The
detailed coating preparation procedure is described in the
Supporting Information. After coating with 1, it can be seen
that the quartz substrates are completely transparent under
nature light. Upon 254 nm UV-light irradiation, the quartzes
exhibit intense yellow-light signals (Figure 4c). The scanning
electron microscopy (SEM) image shows the formation of a
uniform, homogeneous, crack-free, and highly adherent
protective film on the rectangular quartz substrate coated
with hybrid coatings (Figure S5). The coatings can also be
coated on metallic surfaces, as shown in the inset of Figure 4b.
The luminescent coatings show good air and moisture stability.
After the coated quartz was exposed to open air for 1 month,
no noticeable change in the luminescent intensity is observed.
After the coated quartz was heated at 45 °C overnight, the
surface morphology and luminescence intensity of the coatings
show negligible changes (Figure S10). However, the coatings
Figure 3. (a) PXRD patterns of compound 1. (b) FT-IR spectrum of
compound 1. (c) UV−vis absorption spectrum of coatings on quartz.
Inset: Photograph of the quartz coated with the hybrid material. (d)
DOS plot of 0D-Cu4I4(F-tpp)4.
been observed in the PXRD pattern, indicating full
incorporation of the inorganic component in the network
structure. Fourier transform infrared (FT-IR) spectroscopy
shows that the sample exhibited a strong absorption peak at
792 cm−1, corresponding to the absorption peaks of the Si−
O−Si stretching and Si−O−Si bending vibrations, respectively
(Figure 3b). The absorption peaks of the stretching vibrations
of −CH3 and −CH2− in the range of 3000−2800 cm−1 as well
as the CC stretching vibration of a double bond at 1640
cm−1 demonstrate the successful reaction of Cu4I4-dpes with
TEOS via a sol−gel method.
Optical diffuse-reflectance spectra were collected at room
temperature. The dried sample of the OIHC material is
colorless, and the absorption spectrum shows that the OIHC
material exhibits no absorption in the visible-light region. The
C
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Accession Codes
CCDC 1999514 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Author
Wei Liu − School of Chemical Engineering and Technology,
Sun Yat-Sen University, Zhuhai 519082, China;
orcid.org/0000-0002-8543-1605; Email: liuwei96@
mail.sysu.edu.cn
Authors
Hua Tong − School of Chemical Engineering and Technology,
Sun Yat-Sen University, Zhuhai 519082, China
Haibo Li − School of Chemical Engineering and Technology,
Sun Yat-Sen University, Zhuhai 519082, China
Haojun Li − School of Chemical Engineering and Technology,
Sun Yat-Sen University, Zhuhai 519082, China
Cidanpuchi − School of Chemical Engineering and
Technology, Sun Yat-Sen University, Zhuhai 519082, China
Fuchen Wang − School of Chemical Engineering and
Technology, Sun Yat-Sen University, Zhuhai 519082, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00909
Author Contributions
H.T. and H.L. carried out the experiment. H.L., C., and F.W.
contributed to the sample preparation and characterizations.
W.L. wrote the manuscript. All authors discussed the results
and contributed to the final manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The National Natural Science Foundation of China (Grants
21901167 and U20A20233), the Shenzhen Science and
T e c h n o l o g y R e s e a r c h g r a n t ( G r a n t
JCYJ20180307102051326), the Start-up Fund of Sun Yat-
Sen University (76110-18841231), and the Science and
Technology Program of Guangzhou (202102021177) are
greatly acknowledged.
Figure 4. (a) Excitation (red) and emission (black) spectra of
coatings on quartz. λem = 580 nm; λex = 300 nm. Inset: Sol−gel
coating solution under nature and UV light. (b) CIE coordinates of
compound 1. Inset: Coated carbon steel Q235 under 254 nm UV
light. (c) Images of the coated quartz under natural light (top) and
254 nm UV light (bottom).
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00909.
■
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