Multi-component assembly of luminescent rare earth hybrid materials

Multi-component assembly of luminescent rare earth hybrid materials

Accepted Manuscript Multi-component assembly of luminescent rare earth hybrid materials Qiuping Li, Bing Yan PII: S1002-0721(18)30730-0 DOI: https:...

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Accepted Manuscript Multi-component assembly of luminescent rare earth hybrid materials Qiuping Li, Bing Yan PII:

S1002-0721(18)30730-0

DOI:

https://doi.org/10.1016/j.jre.2018.10.001

Reference:

JRE 287

To appear in:

Journal of Rare Earths

Received Date: 4 September 2018 Revised Date:

17 October 2018

Accepted Date: 18 October 2018

Please cite this article as: Li Q, Yan B, Multi-component assembly of luminescent rare earth hybrid materials, Journal of Rare Earths, https://doi.org/10.1016/j.jre.2018.10.001. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Multi-component assembly of luminescent rare earth hybrid materials

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Qiuping Lia, Bing Yan*,b

a) School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, China

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b) School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China ________________________

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*Corresponding author. E-mail address: [email protected] (B. Yan) ABTRACT

This review focuses on the recent research progress in the multi-component assembly of luminescent rare earth hybrid materials, which is based on the luminescent rare earth

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compounds and two or more other building units, including the other photoactive species. It covers the multi-component luminescent rare earth hybrids which was assembled with different (a) organic-inorganic polymeric units, (b) nanoporous units, (c) nanoparticle composites or (d)

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other developing special units. Finally, future challenges and opportunities in this field are

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discussed. Herein it mainly focuses on the work of Yan’s group in recent years. Keywords: Multi-component assembly; rare earth ions; hybrid materials; luminescence

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1. Introduction Rare earth compounds-based optical materials have been widely used in areas of illumination, information display, light communication and so on.1, 2 Because the photoluminescence properties of lanthanide ions (Ln3+) mostly come from the f→f transitions of its 4f orbitals which are well shielded from the environment by the outer 5s2 and 5p6 shells, the Ln3+ ions are usually characterized by narrow band emission and long luminescence lifetime. Since the f→f transition is a parity forbidden transition, most of the Ln3+ ions suffer from weak light absorption(the molar absorption coefficient of the Ln3+ ions is usually smaller than 10 L/(mol cm)). Thus, the primary difficulty to make use of the Ln3+ ions as luminescent materials is the poor light absorption abilities. Fortunately, Weissman3 had discovered early that this problem could be overcome by means of the “antenna effect” within rare earth complexes, which is based on the adsorption of chelated organic ligand and then in a way of intramolecular energy transfer process. Thanks to the powerful coordination ability of Ln3+ ions, numerous rare earth complexes that consist of various sensitizing ligands such as β-diketones, aromatic carboxylic acids and hetero-cyclic molecules were studied over the past half century.4-6 But practical application of the lanthanide compounds is limited largely by its poor photo-stability, thermal-stability and fabricability.7 Therefore, a new concept of “lanthanide-based organic-inorganic hybrid materials” was proposed and have aroused strong interest of researchers over the past decades.8, 9 In general, the luminescent materials prepared by incorporating Ln3+ ions into a well-fabricated hybrid matrix would have better processability, mechanical strength, thermal-stability or even luminescence output than the original lanthanide compounds.10-12 For lanthanide compounds, the existence of organic ligand not only can improve the light absorption ability but also provide an additional opportunity to covalently link them to various matrices through the conjugation of chemical modified ligand. Typically, the Ln3+ ions had been successfully introduced into the sol-gel-derived silica,13 mesoporous silica,14 microporous zeolite,15 semiconductor compound,16 carbon matrix,17 metal-organic framework,18 polymer19 or the composite systems of them.20 Luminescent materials based on this method has been expected to have great potential applications for different fields such as optical amplifiers, sensor materials, light emitting devices, bio-imaging materials, etc.21 Some related reviews and books had been reported by Bünzli,7, 22 Zhang,23 Carlos,24 Sanchez,25 Okamoto,26 Binnemans27 and our group.28 However, the earlier researches were mainly focused on the two-component lanthanide hybrid materials, but fewer were put on the work of three or more component assembly. Although the lanthanide hybrid materials of single functional units have achieved great harvest, the hybrid system can also be introduced more units to accomplish further tuning of luminescence colors or fufill the integration of more functions. Actually, on the basis of the molecular design and chemical modification, it is easy to further introduce some other functional units, other rare earth species or another photoactive species to assemble more complicated multi-component hybrid materials. In this way, we can manipulate the function of materials such as luminescence color or conductive ability to form a more adaptive, outstanding or multi-functional hybrid materials. Here, Fig. 1 gives an illustration to the design and function regulation methods of multi-component luminescent lanthanide hybrids. The existing examples have shown that the multi-component assembly can not simply be seen as a piling-up of different units, but is an effective mean for function regulation. In this review, we give an overview to the assembly of luminescent rare earth hybrid materials which consist of three or more functional units. The common components used in multi-component

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assembly of luminescent lanthanide hybrids are shown in Fig. 1. The multi-component assembly principles for luminescent rare earth hybrids can be summarized as follows: (i) pre-modifying the building unit with silylated groups, vinyl groups or coordination groups is usually essential; (ii) the building blocks, at least some of them can be chemically bonded together; (iii) the assembly could occur in three or even more components systems, the more units can be enclosed, the more properties can be tuned. Here, the attention was mainly focused on the multi-component assembly of luminescent rare earth hybrids with different rare earth compounds, organic matrices, inorganic matrices, nano/micro-porous materials, nanoparticles or other photoactive materials. We hope this review could make a systematic exposition on the progress of photo-functional multi-component hybrid materials which are prepared from the rare earth compounds.

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2. Luminescent rare earth hybrids with multi-component assembly of different organic-inorganic polymeric units. Rare earth hybrid materials based on individual organic or inorganic matrices had been carried out for a long time. However, in order to improve the photostability of rare earth complexes hybrid materials and enlarge its potential applications, the recent research focus was put on to the organic-inorganic polymeric based hybrid materials. Especially, Carlos’s group29-31 had carried out detailed investigations on the preparation of urethanesils-based luminescent rare earth hybrids, which are usually composed of an organic poly(oxyethylene) chain and the covalently bonded inorganic siliceous network via the urethane (−NHC(=O)O–) molecular bridge. The Ln3+ ions can be introduced into the hybrid system easily and characterized by high coordination numbers; the resulted materials had been proven to have high-quantum efficiency, fine-tuning emission chromaticity from red to green, and great potential application in optical-electrical fields. The synthesis of luminescent rare earth hybrid materials go far beyond these, more and more professional researches were focused on the lanthanide hybrid materials which consisted of various inorganic and organic moieties. For organic-inorganic polymer-based multi-component luminescent rare earth hybrids, the Ln3+ ions could coordinate to both the polymer and organically modified inorganic unit together (as shown in Fig. 2), or else only coordinate to one of it (As shown in Fig. 3). Wherein the latter, the organic and inorganic units behave as an integrated ligand to the Ln3+ ions. The coordinated polymer poly methyl methacrylate (PMMA) is the most common co-ligand that had been used for preparing multi-component rare earth hybrids. Sheng et al.32 had modified the photoactive ligand PHA (O-phthalic anhydride) with silane coupling agent APTES ((3-aminopropyl) triethoxysilane) and chosen the PMMA as the co-ligand coordinating to Eu3+ or Tb3+. Thereafter, they fabricated several novel rare earth organic/inorganic/polymeric hybrids Eu/Tb-(PHA-Si)-PMMA (Fig. 2) through the hydrolysis of methyl methacrylate (MMA) monomer, the tetraethoxysilane (TEOS) and the silanized PHA ligand in the presence of the initiator BPO (benzoyl peroxide) and the corresponding Ln3+ ions. The results prove that the introduction of the organic polymer PMMA could bring an obvious improvement to the luminescent properties of the hybrid systems. In another work, Sheng et al.33 had fabricated a series of Tb3+ and inert lanthanide ions (La3+, Gd3+, Y3+) co-doped organic-inorganic-polymeric hybrids, wherein, the APTES modified organic ligand 5-sulfosalicylic acid (SSA) acted as an functionalized molecular bridge (SSA-Si) which could coordinate to both the Tb3+ and inert lanthanide ions (La3+, Gd3+, Y3+) to form luminescent centers. The organic polymer PMMA was introduced to replace the coordinated water molecules and also

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acted as the energy absorbing “antenna”. They had studied the co-luminescence effect between Tb3+ ion and the other Ln3+ ions, founded that the Tb-La coexisting in organic-inorganic-polymeric hybrid systems possessed the highest co-luminescence phenomenon. Li et al.34 had presented a novel path to incorporate rare earth complexes into some composite matrices which consisted of organic PMMA and inorganic Si-Ti oxide by employing the 3-(triethoxysilyl)-propyl isocyanate (TESPIC) modified 3,5-dihydroxybenzoic acid (DHBA) as an conjugated molecule. The titanium alkoxide was covalently graft onto the Si-O network, and finally they obtained a four-component luminescent hybrid material Eu(Ti-DHBA-Si)3PMMA via a sol-gel process. Besides, the method mentioned above for the design and synthesis of hybrid materials could be easily applied to other PMMA-based or another coordinated polymer-based organic-inorganic multi-component rare earth hybrids.35, 36 As mentioned before, the Ln3+ ions could only coordinate to the selected ligand or polymer unit in the hybrid materials. Polymers which bear active groups such as hydroxyl, amide, carboxylic etc. could be easily attacked by the silane cross-linking reagent TESPIC, and then react with the other organic silicon compound during the sol-gel process. Wang et al.37 had synthesized two kinds of silylated polymer precursor PAM-Si and PEG-Si through the grafting reaction between PAM (polyallylamine) / PEG (poly(ethylene glycol)) and TESPIC, and then let it react with the silylated rare earth compound. Finally, two kinds of ternary hybrid materials RE-BFPP-Si-PAM or RE-BFPP-Si-PEG (Fig. 3) were obtained, in which the polymer moieties connected with the silicon-oxide networks but did not link to the Ln3+ ions directly. In another report,38 the acrylamide monomer was modified by (3-chloropropyl)trimethoxysilane (CPMS) and then was polymerized to form another kind of PAM-Si, which was then used to construct multi-component hybrid materials together with the TESPIC modified 5-hydroxyisophthalic acid (HIPA) and rare earth (Eu, Tb) elements. The multi-component hybrid materials could also be synthesized via the molecule self-assembly method without the silylated reaction. A paper related to this method had reported several four-component rare earth hybrid materials, in which the pyridine dicarboxylate ligands acted as the molecular bridge both coordinated to Ln3+ and Al3+ / Ti4+ in the gels. While the polymer unit polyacrylic acid (PA) was introduced to the hybrid system through the coordination reaction between the dicarboxylates and Al3+ / Ti4+ ions.39 The multi-component assembly method has also been proven an effective way for synthesizing rare earth hybrid nanocomposites comprising organic polymer and inorganic units. Zheng et al.40 had successfully encapsulated various Ln3+ ions doped silica hybrid nanoparticles into a well-designed cylindrical polymer brush, to form a series of core-shell nano-hybrids. The resulted materials had been found to have high stability, as well as a satisfying solubility in water and alcohols. Conversely, Yuan et al.41 filled the poly(4-vinylpyridine) and 1,10-phenanthroline co-coordinated rare earth ions into a hollow mesoporous silica sphere according to the ship-in-a-bottle approach. Rodrigues et al.42 had reported very interesting multi-component rare earth hybrid materials which were built by self-assembly of Tb3+ / Eu3+ complexes monolayer on the PEG functionalized Si surface, leading to a thermometer whose thermal sensitivity was up to 1.43% K–1, cycle-recycle reliability was 98.6% and temperature uncertainty was less than 0.3 K. Wang et al.43, 44 had encapsulated the rare earth complexes functionalized silica nanoparticles into isotactic polypropylene / polyacrylonitrile nanofibers via electrospinning technique, the resulted ternary component hybrid materials were believed to have great potential applications in optical devices.

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Besides, there were also some other reports about the multi-component assembly examples of the organic-inorganic polymeric luminescent rare earth hybrid materials.45, 46 For instance , the newly developed luminescent polymer hydrogels which usually consisted of two or more rare earth species had been proven to be an ideal method for making materials of multi-color photoluminescence emissions.47, 48 Thus, the organic-inorganic polymeric luminescent rare earth hybrid materials are still worth exploring.

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3. Luminescent rare earth hybrids with multi-component assembly of different nanoporous units The controllable encapsulation of rare earth compounds into porous solids such as mesoporous silicates, microporous crystalline aluminosilicates or the other porous matrices has attracted great research interest in recent years.49, 50 This is mainly because some porous materials not only can provide quite stable chemical environment for the rare earth compounds, but also can effectively enhance the photoluminescent properties of the corresponding Ln3+ ions. Meanwhile, the rare earth compounds can be easily introduced both inside and outside of the selected porous matrices. Thus, it has caught people's interest to prepare multi-component luminescent rare earth hybrids with various porous matrices via the host-guest assembly method recently. The synthesis of mesoporous silicate-based rare earth hybrid materials refers to the post-synthesis modification of a mesoporous materials or the in-situ functionalization during the synthesis procedures of them. In a report51 about the ternary rare earth functionalized SBA-15 / polymer hybrids, the TESPIC modified 2-henoyltrifluoroacetone (TTA-Si) ligand was introduced into the SBA-15 matrix by co-condensation reaction with the modified TTA-Si and tetraethoxysilane (TEOS) together during the sol-gel procedures. Then the final materials were prepared by mixing the Ln3+ ions, the as-prepared PMMA precursor and the aforementioned TTA-Si modified SBA-15 together, in which the Ln3+ ions coordinated to both the PMMA and TTA moieties. The resulted ternary rare-earth mesoporous polymeric hybrid materials were chemically bonded and had stronger luminescent properties than the binary hybrid materials. The polymer chain could also be covalently linked onto the surfaces of mesoporous silicates at first. Li et al.52 had introduced the TESPIC modified acrylamide into a SBA-16 backbone through co-hydrolysis and co-condensation reactions, and then initiated a polymerization reaction of the amide monomer within the pores of SBA-16 to form a polyacrylamide (PAM) modified SBA-16 matrix. After introducing the Eu3+ / Tb3+ ions and the typical ligand 1,10-phenanthroline (phen), a series of ternary luminescent rare earth hybrids Ln(S16-PAM-Si)3phen were obtained, in which the organic polymer acted as a flexible linker between the mesoporous framework and the lanthanide complexes. Functionalization of the pre-synthesized silicates with commercialized oxosilane couple agents or the other well-designed organic silane bearing amino group, vinyl group or coordination sites had yet been proven another methods for constructing multi-component rare earth hybrids. Zheng et al.53 had modified the as-prepared MCM-41 with vinyltrimethoxysilane to found MCM-41-vinyl and synthesized several kinds of polymerizable europium complexes Eu(TTA)3L2, and then successfully assembled a series of ternary europium complexes / poly(ionic liquid) / MCM-41 luminescent hybrids through an in situ polymerization of polymerizable europium complexes, polymerizable ionic liquids, and vinyl-modified MCM-41. The synthetic scheme and predicted structure of these ternary rare earth hybrid materials are outlined in Fig. 4, together with the photograph of the resulted materials under daylight and UV Lamp. In another work reported by Wang et al.,54 a novel 2D lanthanide

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coordination polymer was covalently bonded to amine-modified SBA-15 and MCM-41 through the formation of Schiff-base groups. The resulted hybrid materials showed high thermal and photoluminescence stability, as well as a remarkable chemical resistance to boiling water / acidic / alkaline medium. There are also many interesting works about the multi-component assembly of luminescent rare earth hybrids involving the mesoporous silicates and polymer units.55–57 Besides, the other inorganic amorphous matrices such as Ti–O or Al–O networks could also be introduced into the ordered mesoporous Si–O network through the hydrolysis cross-linking reaction. Li et al.58, 59 had dedicated several works on the multi-component assembly of luminescent hybrids with titania / alumina oxide, SBA-15 supporter and rare earth complexes. Zeolites are kinds of microporous aluminosilicates tetrahedron that have abundance channels and cavities where can be easily filled by Ln3+ ions, rare earth compounds or the other functional units, thus attracted considerable interest for the preparation of novel rare earth hybrid materials.60 The ion exchange, ship-in-bottle method and surface modification are the most commonly means for the multi-component assembly of zeolite-based rare earth hybrids. With these methods, Hao et al.61 had successfully built a ITO glass substrate supported poly ethyl methacrylate (EMA) and poly 4-vinylpyridine (P4VP) / rare earth complexes / zeolite A hybrid films. In another works,62 they had synthesized eight host-guest multi-component hybrids by first embedding rare earth complexes (Eu(TTA)n or Tb(TAA)n) into the cages of zeolite A, and then grafting another kind of rare earth complexes onto the surface of zeolite A via a silane coupling agent. Finally, a series of white light-emitting materials were prepared, the three-component system consisted of a blue-emitting zeolite A, a red-emitting europium complex and a green-emitting terbium complex. Zhang et al.63 had reported a thermally stable white light emitting hybrid materials which consisted of Eu3+ complex / nanozeolite L / luminescent glass components, and successfully fabricated warm white LEDs by simply combining it with a NUV-Chip-On-Board substrate. In order to explore the possibility and feasibility of more complicated assembly, Chen et al.64 had prepared a rare earth complex loaded zeolite A/L and introduced a second photoluminescent phosphor polyoxometalate (Na9LnW10O36·32H2O(LnW10, Ln=Eu, Tb, Sm or Dy)), and then built several kinds of multi-component hybrids LnW10-IM-[ZA/L*Eu-TTA] and LnW10-IM-[ZA/L*Tb-TAA] (Ln = Eu, Tb, Sm or Dy) through an ionic liquid linker. The preparation scheme for such double luminescent centers functionalized rare earth hybrid materials is shown in Fig. 5. From these cases, we can see that the multi-component assembly of microporous zeolites with different rare earth compounds and the other units is an efficient way of tuning the photoluminescent properties of the rare earth hybrids. This had also been proven by many other reports.65–67 In addition, Sun et al.68 had reported a rare earth complexes inside-outside double functionalized zeolite A system which possessed a selective fluorescence quenching effect for metal ions, especially for Fe3+ ions. All of these further prove the necessity and significance to do the research of multi-component assembly of luminescent rare earth hybrid materials. Furthermore, different nanoporous matrices could be joined together to found a more complicated hybrid materials. Chen et al.69 had successfully built several four components hybrids by linking the 1,10-phenanthroline surface functionalized SBA-15 and the para-hydroxybenzoic acid surface functionalized rare earth complex loaded zeolite A/L through the coordination reactions with Ln3+ ions. In conclusion, the important way of constructing the chemically bonded luminescent rare earth hybrids with mesoporous silicates or microporous aluminosilicates is to incorporate the organic components into its pores or surfaces, and then tether each part together via the

well-designed molecular bridge.

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4. Luminescent rare earth hybrids with multi-component assembly of different nanoparticle composites The assembly of rare earth compounds with photoactive or magnetic units such as TiO2, ZnO, ZnS, GdS, GaN, carbons, Fe3O4, upconversion nanoparticles, etc. together with some special functional units could easily expend the application range of luminescent rare earth hybrids to the fields of photocatalysis, medical imaging, biosensor and so on. Nanoparticles with size-dependent photoluminescence were usually chosen as the building units of rare earth hybrid materials, because it could play a synergistic role in the photophysical properties with the rare earth compounds. Shao et al.70 had reported a ternary luminescent hybrid materials by covalently linking the rare earth complexes to a polymer-wrapped ZnO core-shell nanoparticle substrate, the scheme for preparing this ZnO-MAA-HEMA-RE-phen hybrid is shown in Fig. 6. In another works,71 they prepared a polymer-wrapped ZnO nanoparticle and introduced it into the SBA-15 via an in-situ co-hydrolysis and co-condensation procedure, and then with a coordination reaction between the residual coordination site of rare earth complexes and the carboxylate groups of the pre-synthesized polymer/ZnO/SBA-15 hybrid matrix. Finally, four-component assembled photoluminescent hybrid materials were obtained. Furthermore, they had successfully got a white luminescence system based on multiple-component assembly methods.72 Duan et al.73 had reported another example of white light LED application which involved the multi-component assembly of rare earth ions activated ZnO and metal-organic frameworks. Besides, some other works had also fulfilled the luminescence manipulation through the multiple-component assembly based on the rare earth compounds and ZnO nanoparticles together.74, 75 The ZnS and CdS semiconductors were also proven to be photo-active building units for constructing the rare earth hybrids with multi-component. It had been used to prepare white luminescence materials by linking a Eu3+ beta-diketonate with them together through an ionic liquid linkage.76 Another semiconductor nanoparticle that had held researchers’ attention is nano-scaled TiO2 particles. Zhao et al.77 had synthesized a multi-component hybrid by tethering the TiO2 with rare earth complex through a double cross-linked siloxane. For comparison, they had introduced CdS quantum dot to compare the influence of additional photoactive units. Khoshnavazi et al.78 had found a photocatalytic activity enhancement behavior in the rare earth doped TiO2 / sandwich-type polyoxometalates hybrid systems. Besides, GaN matrix had also been proven to be applicable matrices for constructing rare earth hybrid luminescent materials.79, 80 In an example,81 the GaN and SBA-15 were functionalized by the TESPIC modified organic ligand TTA separately, and then were assembled together with the rare earth elements via the self-assembly methods through the coordination bond between Ln3+ ions and TTA moieties, to make up a ternary luminescent hybrid. In a word, the binding of other photoactive species and rare earth compounds is good cut-in for exploring the tuning of spectrum. The recent development in life sciences demands more accurate technology to sense or monitor the chemical substances and vital processes occurring in vivo. Hence, it brings greater opportunities for scientists to design and synthesize related luminescent markers which could meet the demands through multi-component assembly method.7, 82 Shao et al.83 had synthesized a magnetic / mesoporous silica core-shell nanosphere ([email protected]), and linked it with europium(III) tetrakis(β-diketonate) complexes through the ionic liquid 1-methyl-3-[3-(tri-methoxy-silyl)propyl]

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imidazolium chloride linkage, the assembly method and the resulted material are shown in Fig. 7. In another work,84 they had introduced a polymer modified ZnO to be as the second functional unit of a multifunctional nanocomposite. In another work reported by Wang et al.85, the Fe3O4 nanoparticle was incorporated into an iodine-containing europium complex by seed emulsifier-free polymerization, the resulted nanocomposite was a typical ternary rare earth hybrid material which was suitable for computed X-ray tomography, magnetic resonance imaging and optical imaging. This core-shell assembly method was also used by Zhu et al.86 They had constructed a magnetic, fluorescent and thermo-responsive colloidal nanoparticle by incorporating the Fe3O4 and Eu3+ complex (Eu(AA)3Phen) into a poly(styrene-N-isopropylacrylamide) shell. Other interesting multiple-assembly of luminescent rare earth hybrids was related to the upconverting rare-earth nanoparticles. Yi et al.87 had reported a water-soluble core/shell/shell nanoparticles with significant enhancement of upconversion fluorescence, in which the NaYF4:Yb,Er(Tm) core was coated with an undoped NaYF4 shell at first, and then was further rendered by a layer of amphiphilic polymer, the resulted nanoparticle was proven to be a suitable probe material for bio-applications. Wang et al.88 had synthesized a kind of dual-modality imaging contrast agent which contained two primary functions (upconverting fluorescence and magnetic resonance imaging property) by coating the upconverting rare-earth nanoparticles (NaYF4:Yb (30%), Er(5%)/La(5%) and NaYbF4:Tm (2%)) with an paramagnetic rare earth complex and polyethylene glycol shells. In addition, Ge et al.89 had tethered a terbium complex onto the mesoporous SiO2-coated NaYF4:Yb,Er nanoparticle to form a novel up-conversion and down-conversion luminescent nanoparticle which could be used both in vitro bioimaging and sensing of temperature. The assembly of multiple-functional luminescent nanoparticle can also be achieved by the use of heterometallic rare earth complexes. For instance, Li et al.90 had prepared several bifunctional heterometallic Ln3+-Gd3+ (Ln = Eu, Tb) complexes doped silica microspheres for the purposes of luminescence and MRI contrast agent. Many other kinds of nanoparticles had also been used for building units of multi-component luminescent rare earth hybrid materials such as Au nanoparticle,91 carbon nanotube,92 carbon dot,93 etc. However, there are still many problems remaining to be worked out before the multi-component luminescent rare earth hybrids can be widely used in practice.

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5. Luminescent rare earth hybrids with multi-component assembly of different other developing special units. In addition to the above mentioned works, many other special units had also been used to build multi-component luminescent rare earth hybrid materials. Chen et al.94 had reported a novel Eu3+/ LAPONITE®(Lap)-based organic / inorganic hybrid material which showed an interesting fluorescent quenching effect to Cu2+, the fluorescence could then be recovered by the glutathione, showing an "off-on" process with regard to glutathione detection. The hybrid material had further been made into a transparent hydrogel film which could still retained its previously-observed sensing ability. In another work, Kemal et al.95 had assembled the conjugated polymer PVK and PLGA-PEG with both a luminescent rare-earth complex and a magnetic nanoparticle, giving rise to materials that were suitable for biological imaging applications. Recently, a class of crystalline porous materials formed by the self-assembly of polydentate bridging ligands and metal-connecting points, the metal-organic frameworks (MOFs), have been found to have great potential applications for building optical materials.96–98 The MOFs can be either used as a host matrix to carry lanthanide complexes or chemically modified via post-synthetic

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method (PSM) to enclose additional functional units with sophisticated chemical and physical properties. Of course, it has become an advisable matrix material for the assembly of multi-component luminescent rare earth hybrids.99 In an work reported by Lu et al.,100 the MOF-253 was first functionalized by rare earth complex via PSM and then an organic polymer was introduced to achieve the ternary assembly of rare earth complex / MOF / polymer hybrid materials, which was further assembled onto a GaN chip to white LED. In another work,101 the indium 2,2’-bipyridine-5,5’-dicarboxylate based MOF was introduced with Ln3+ (Eu3+, Tb3+ and Sm3+) via PSM and then loaded with an organic polymer directly through a coordination reaction, the resulted materials were ternary hybrids which could be assembled onto an UV LED lamp to make white light LED. The assembly scheme of them is shown in Fig. 8 together with the emission spectra and CIE diagram of the LED lamp. The ZIF-8 MOF was also used to prepare multi-component luminescent rare earth hybrids by Liu et al.,102 a series of hybrid polymer films were prepared by assembling the rare earth complexes modified ZIF-8 with the co-polymer PEMA-PVPD together. The luminescence color could be easily tuned by adjusting the ratios of the blue (for ZIF-8), red (for Eu3+) and green (for Tb3+), and even to make white light by integrating the emission of both Eu3+ and Tb3+ into a hybrid system. The multi-component assembly of rare earth complex / polymer / MOF can also be used to prepare luminescent rare earth hybrids that had sensing property103 and go far. The inorganic quantum dots could also be used to assemble the luminescent rare earth MOF hybrids. Typically, the zinc oxide (ZnO) had been introduced into the framework of lanthanide doped zinc centered MOFs by Duan et al., 73 forming a series of ternary hybrids [email protected](pdc)-Ln (Ln = Eu, Tb, Sm, Dy). These Eu3+ ion activated [email protected](pdc) could be applied onto the commercially available UV-LED lamp which showed white lights under ultraviolet excitation. Besides, a ternary europium complex / ZnO / MOF hybrid had been found and used to fabricate the ppb-level sensing platform for volatile aldehyde gases in vehicles.104 The classic TiO2 semiconductor had also been used to prepare luminescent rare earth MOF hybrids. Xu et al.105 had prepared several rare earth complexes / titania / MOF (Al-MIL-53-COOH) multi-component hybrid systems, one of the europium complexes functionalized hybrid materials had been found to have the white photoluminescence property. In another work, Zhu et al.106 had studied the photocatalytic properties of a composite material composed of TiO2 and a titanium-based metal-organic framework. The emission color of it could be further tuned by simply doping different Ln3+ (Eu3+, Tb3+, and Sm3+) ions to form the ternary [email protected](Ti)@TiO2 hybrids (as shown in Fig. 9). The introduction of TiO2 to some rare earth MOF hybrids had also be used to develop sensing materials by Weng et al.107, the combination of anionic Bio-MOF-1 (Zn8(ad)4(BPDC)6O2Me2NH2) and samarium complex doped TiO2 ([email protected]) could produce a novel ratio-dependent oxygen sensing material. Moreover, some other special units were also included to assemble luminescent rare earth MOF hybrids. For instance, the IRMOF-3 was synthesized directly on the silane coupling agent (3-isocyanatopropyltriethoxysilane) modified mesoporous silicate SBA-15 precursor (Si-SBA-15), and then the Ln3+ ions were introduced into the SBA-15-Si-IRMOF-3 host through the coordination reaction to assemble a quaternary luminescent rare earth hybrids (As shown in Fig. 10).108 The carboxyl-modified SiO2 microsphere was also chosen to fabricate a ternary [email protected]@ZIF-8 hybrid, which was proved to have highly selective and sensitive sensor capacity to detect Cu2+ ions in aqueous solution.109 Analogously, after packing up the europium-MOF layer onto a nonwoven

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polypropylene (PP) surfaces and following by a polydimethylsiloxane coating treatment, a multi-component luminescent rare earth hybrid fiber was obtained which showed highly sensitive ratiometric oxygen sensor property.110 Besides, Xu et al. 111 had adopted optical active carbon dots to fabricate ternary hybrid ( Eu3+/[email protected]) which had the application for ratiometric and colorimetric fluorescent probe properties to Hg2+ ions. Furthermore, Zhou et al.112 had designed a ratiometric multiplexed barcodes based on the hybrid system of rare earth complexes / MIL-100 (In) film / organic dyes.

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6. Summary More recently, we have developed a great interest in the construction of rare earth hybrid materials through the multi-component assembly methods. Our groups have enclosed the mesoporous silicate,51,55 microporous zeolite,64–69 inorganic quantum dots,70–76 semiconductor particles,79–81 magnetic nanoparticles,83,84 silicon spheres,90,109 polyoxometalate,66,75 MOFs,98–112 polymers,51,70 carbon nanotubes,92 carbon dots,111 ionogels74, etc. to be the building units for designing and synthesizing multi-component luminescent rare earth hybrid materials. With the union use of these materials, we have reported lots of multi-component luminescent rare earth hybrid materials, such as inorganic-organic polymeric hybrids,32,39 host-guest assembly hybrids with porous units,56,61 core-shell assembly hybrids,70,109 nanocomposites,84,108 hybrid gels,39,76 polymer hybrids101–103. Our group first focused on the designing and enlarging of the family of luminescent rare earth materials, and we now not only keep continuing interest in it but also try to extend our interests to their application in fields of bio-sensing, chemical-sensing, white light emitting device, intelligent marker and so on. Although hundreds of examples of multi-component luminescent rare earth hybrid materials had been reported by teams all over the world, there are still some problems of micro-structure, synthesis strategy and function collaboration that worth to explore. Therefore, our group has shifted to use the crystalline MOFs as building blocks to synthesize multi-component rare earth hybrid via host-guest assembly method. We will continue exploring the controlled preparation method, formation mechanism of the microstructure and the luminescence enhancement phenomena. Especially, the function collaboration is worth studying and discussing in-depth in future, because it concerns the practical use of the luminescent rare earth hybrid materials. But the existing experiments to date is not sufficient to advance with the urgency needs. Thus, there are still many challenges and opportunities for us to introduce more special units to assemble multi-component luminescent rare earth hybrid materials and tune their properties to see the broad range of practical applications. Foundation item: Project supported by the National Natural Science Foundation of China (21571142), the Developing Science Fund of Tongji University, the Natural Science Foundation of Zhejiang Province (LQ14B010001), and the Natural Science Foundation of Ningbo, China (2016A610105). References 1. Rare-earth-doped fiber lasers and amplifiers. Edited by Digonnet MJ. New York: Marcel Dekker, Inc., 2001. 2. Song X, Chang M, Pecht M. Rare-earth elements in lighting and optical applications and their recycling. JOM. 2013;65(10):1276.

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55. Cuan J, Yan B. Multi-component assembly and photophysical properties of europium polyoxometalates and polymer functionalized (mesoporous) silica through a double functional ionic liquid linker. Dalton Trans. 2013;42(39):14230. 56. Gu YJ, Yan B, Li YY. Ternary europium mesoporous polymeric hybrid materials Eu(β-diketonate)3pvpd-SBA-15(16): host–guest construction, characterization and photoluminescence. J Solid State Chem. 2012;190:36. 57. Li Y, Wang JL, Chain W, Wang X, Jin Z, Li XQ. Coordination assembly and characterization of europium(III) complexes covalently bonded to SBA-15 directly functionalized by modified polymer. RSC Adv. 2013;3(33):14057. 58. Li YJ, Yan B. Preparation, characterization and luminescence properties of ternary europium complexes covalently bonded to titania and mesoporous SBA-15. J Mater Chem. 2011;21(22):8129. 59. Yan B, Li YJ. Photoactive lanthanide (Eu3+, Tb3+) centered hybrid systems with titania (alumina)-mesoporous silica based hosts. J Mater Chem. 2011;21(45):18454. 60. Wang Y, Li HR. Luminescent materials of zeolite functionalized with lanthanides. CrystEngComm. 2014;16(42):9764. 61. Hao JN, Yan B. Hybrid polymer thin films with a lanthanide–zeolite A host–guest system: coordination bonding assembly and photo-integration. New J Chem. 2014;38(8):3540. 62. Hao JN, Yan B. Photofunctional host-guest hybrid materials and thin films of lanthanide complexes covalently linked to functionalized zeolite A. Dalton Trans. 2014;43(7):2810. 63. Zhang JH, Gong SM, Yu JB, Li P, Zhang XJ, He YW, et al. Thermally stable white emitting Eu3+ [email protected]@luminescent glass composite with high CRI for organic-resin-free warm white LEDs. ACS Appl Mater Interfaces. 2017;9(8):7272. 64. Chen L, Yan B. Multi-component assembly and luminescence tuning of lanthanide hybrids through the inside–outside double modification of zeolite A/L. New J Chem. 2015;39(5):4154. 65. Chen L, Yan B. Multi-component lanthanide hybrids based on zeolite A/L and zeolite A/L-polymers for tunable luminescence. Photochem Photobiol Sci. 2015;14(2):358. 66. Chen L, Yan B. Novel multi-component hybrids through double luminescent lanthanide unit functionalized zeolite L and titania. Spectrochim Acta, Part A. 2015;151:100. 67. Chen L, Yan B. Multi-color luminescence of hybrids based with lanthanide functionalized zeolite A and titania. Colloid Polym Sci. 2015;293(6):1847. 68. Sun NN, Yan B. Lanthanide complex inside–outside double functionalized zeolite A hybrid materials for luminescence sensing. New J Chem. 2016;40(8):6924. 69. Chen L, Yan B. Multi-component assembly and luminescence tuning of lanthanide hybrids based with both zeolite L/A and SBA-15 through two organically grafted linkers. Dalton Trans. 2014;43(37):14123. 70. Shao YF, Yan B. Photofunctional hybrids of rare earth complexes covalently bonded to ZnO core–shell nanoparticle substrate through polymer linkage. Dalton Trans. 2012;41(24):7423. 71. Shao YF, Yan B, Jiang ZY. Multicomponent assembly of luminescent hybrid materials of ZnO-lanthanide polymer complex functionalized SBA-15 mesoporous host by chemical bonds. RSC Adv. 2012;2(24):9192. 72. Shao YF, Yan B. Multi-component hybrids of surfactant functionalized europium tetrakis (β-diketonate) in MCM-41(m) and polymer modified ZnO for luminescence integration. Microporous Mesoporous Mater. 2014;193:85. 73. Duan TW, Yan B. Lanthanide ions (Eu3+, Tb3+, Sm3+, Dy3+) activated ZnO embedded zinc

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2,5-pyridinedicarboxylic metal–organic frameworks for luminescence application. J Mater Chem C. 2015;3(12):2823. 74. Mei Y, Lu Y, Yan B. Soft materials composed with lanthanide (Eu3+, Tb3+) beta-diketonates and ZnO nanoparticles through ionic liquid linkage to integrate white luminescence. J Photochem Photobiol, A. 2014;280:1. 75. Yan B, Shao YF. Multicomponent hybrids with surfactant-encapsulated europium polyoxometalate covalently bonded ZnO and tunable luminescence. RSC Adv. 2014;4(7):3318. 76. Mei Y, Lu Y, Yan B. Soft hybrids of Eu3+ beta-diketonates and MS (M = Zn, Cd) nanoparticles using mercapto-ionic liquid linkage for white luminescence integration. New J Chem. 2013;37(9):2619. 77. Zhao Y, Yan B. Photoluminescent properties of novel rare earth organic-inorganic nanocomposite with TiO2 modified silica via double crosslinking units. Photochem Photobiol. 2012;88(1):21. 78. Khoshnavazi R, Sohrabi H, Bahrami L, Amiri M. Photocatalytic activity enhancement of TiO2 nanoparticles with lanthanide ions and sandwich-type polyoxometalates. J Sol-Gel Sci Technol. 2017;83(2):1. 79. Li QP, Yan B. Luminescent GaN semiconductor based on surface modification with lanthanide complexes through an ionic liquid bridge. RSC Adv. 2012;2(29):10840. 80. Zhao Y, Yan B. Rare earth hybrid materials of organically modified silica covalently bonded to a GaN matrix: multicomponent assembly and multi-color luminescence. Dalton Trans. 2012;41(17):5334. 81. Zhao Y, Yan B. Eu3+, Tb3+/β-diketonate functionalized mesoporous SBA-15/GaN composites: Multi-component chemical bonding assembly, characterization, and luminescence. J Colloid Interface Sci. 2013;395:145. 82. Yu JB, Rong Y, Kuo CT, Zhou XH, Chiu DT. Recent advances in the development of highly luminescent semiconducting polymer dots (Pdots) and nanoparticles (CPNs) for biological imaging and medicine. Anal Chem. 2016;89(1):42. 83. Shao YF, Yan B, Li QP. Magnetic mesoporous silica nanosphere supported europium(III) tetrakis(β-diketonate) complexes with ionic liquid compounds as linkers. Eur J Inorg Chem. 2013;2013(3):381. 84. Yan B, Shao YF. Multifunctional nanocomposites of lanthanide (Eu3+, Tb3+) complexes functionalized magnetic mesoporous silica nanospheres covalently bonded with polymer modified ZnO. Dalton Trans. 2013;42(26):9565. 85. Wang X, Tu MQ, Yan K, Li PH, Pang L, Gong Y, et al. Trifunctional polymeric nanocomposites incorporated with Fe3O4/iodine-containing rare earth complex for computed X-ray tomography, magnetic resonance, and optical imaging. ACS Appl Mater Interfaces. 2015;7(44):24523. 86. Zhu HE, Tao J, Wang WH, Zhou YJ, Li PH, Li Z, et al. Magnetic, fluorescent, and thermo-responsive Fe3O4/rare earth incorporated poly(St-NIPAM) core–shell colloidal nanoparticles in multimodal optical/magnetic resonance imaging probes. Biomaterials. 2013;34(9):2296. 87. Yi GS, Chow GM. Water-soluble NaYF4:Yb,Er(Tm)/NaYF4/polymer core/shell/shell nanoparticles with significant enhancement of upconversion fluorescence. Chem Mater. 2007;19(3):341. 88. Wang Y, Ji L, Zhang BB, Yin PH, Qiu YY, Song DQ, et al. Upconverting rare-earth nanoparticles with a paramagnetic lanthanide complex shell for upconversion fluorescent and

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magnetic resonance dual-modality imaging. Nanotechnology. 2013;24(17):175101. 89. Ge XQ, Sun LN, Dang S, Liu JL, Xu YX, Wei ZW, et al. Mesoporous upconversion nanoparticles modified with a Tb(III) complex to display both green upconversion and downconversion luminescence for in vitro bioimaging and sensing of temperature. Mikrochim Acta. 2015;182:1653. 90. Li YY, Yan B, Li QP. Bifunctional heterometallic Ln3+–Gd3+ (Ln = Eu, Tb) hybrid silica microspheres: luminescence and MRI contrast agent property. Dalton Trans. 2013;42(5):1678. 91. Li HQ, Yang JH, Deng QQ, Dou SM, Zhao WW, Lin C, et al. Au [email protected]@europium coordination polymer nanocomposites for enhanced fluorescence and more sensitive monitoring reactive oxygen species. Sci China Mater. 2018;61(3):401. 92. Li QP, Yan B. Multi-walled carbon nanotube-based ternary rare earth (Eu3+, Tb3+) hybrid materials with organically modified silica–oxygen bridge. J Colloid Interface Sci. 2012;380(1):67. 93. Wang Y, Čépe K, Zbořil R. UV light-switchable transparent polymer films and invisible luminescent inks based on carbon dots and lanthanide complexes. J Mater Chem C. 2016;4(30):7253. 94. Chen X, Wang YR, Chai R, Xu Y, Li HR, Liu BY. Luminescent lanthanide-based organic/inorganic hybrid materials for discrimination of glutathione in solution and within hydrogels. ACS Appl Mater Interfaces. 2017;9(15):13554. 95. Kemal E, Peters R, Bourke S, Fairclough S, Bergstrom-Mann P, Owen DM, et al. Magnetic conjugated polymer nanoparticles doped with a europium complex for biomedical imaging. Photochem Photobiol Sci. 2018;17(6):718. 96. Zhang DN, Zhou Y, Cuan J, Gan N. A lanthanide functionalized MOF hybrid for ratiometric luminescence detection of an anthrax biomarker. CrystEngComm. 2018;20(9):1264. 97. Zhou Y, Yang Q, Zhang DN, Gan N, Li QP, Cuan J. Detection and removal of antibiotic tetracycline in water with a highly stable luminescent MOF. Sens Actuators, B 2018;262:137. 98. Shen X, Yan B. Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange. J Colloid Interface Sci. 2016;468:220. 99. Lu Y, Yan B. A novel luminescent monolayer thin film based on postsynthetic method and functional linker. J Mater Chem C. 2014;2(28):5526. 100. Lu Y, Yan B. Lanthanide organic–inorganic hybrids based on functionalized metal–organic frameworks (MOFs) for a near-UV white LED. Chem Commun. 2014;50(97):15443. 101. Wu JX, Yan B. Lanthanides post-functionalized indium metal–organic frameworks (MOFs) for luminescence tuning, polymer film preparation and near-UV white LED assembly. Dalton Trans. 2016;45(46):18585. 102. Liu C, Yan B. Photoactive hybrid polymer films incorporated with lanthanide complexes and ZIF-8 for selectively excited multicolored luminescence. Eur J Inorg Chem. 2015;2015(2):279. 103. Shen X, Yan B. Polymer hybrid thin films based on rare earth ion-functionalized MOF: photoluminescence tuning and sensing as a thermometer. Dalton Trans. 2015;44(4):1875. 104. Xu XY, Yan B. Eu(iii)-functionalized [email protected] heterostructures: integration of pre-concentration and efficient charge transfer for the fabrication of a ppb-level sensing platform for volatile aldehyde gases in vehicles. J Mater Chem A. 2017;5(5):2215. 105. Xu XY, Yan B. Novel photofunctional hybrid materials (alumina and titania) functionalized with both MOF and lanthanide complexes through coordination bonds. RSC Adv. 2014;4(73):38761.

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106. Zhu SY, Yan B. Photofunctional hybrids of TiO2 and titanium metal–organic frameworks for dye degradation and lanthanide ion-tuned multi-color luminescence. New J Chem. 2018;42(6):4394. 107. Weng H, Xu XY, Yan B. Novel multi-component photofunctional nanohybrids for ratio-dependent oxygen sensing. J Colloid Interface Sci. 2017;502:8. 108. Lian X, Yan B. Multi-component luminescent lanthanide hybrids of both functionalized IRMOF-3 and SBA-15. New J Chem. 2015;39(8):5898. 109. Liu C, Yan B. Highly effective chemosensor of a luminescent [email protected] [email protected] heterostructured composite for metal ion sensing. RSC Adv. 2015;5(123):101982. 110. Xu XY, Yan B. Nanoscale LnMOF-functionalized nonwoven fibers protected by a polydimethylsiloxane coating layer as a highly sensitive ratiometric oxygen sensor. J Mater Chem C. 2016;4(36):8514. 111. Xu XY, Yan B. Fabrication and application of a ratiometric and colorimetric fluorescent probe for Hg2+ based on dual-emissive metal-organic framework hybrids with carbon dots and Eu3+. J Mater Chem C. 2016;4(7):1543. 112. Zhou Y, Yan B. Ratiometric multiplexed barcodes based on luminescent metal–organic framework films. J Mater Chem C. 2015;3(32):8413.

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Fig. 1. The viable assembly units of multi-component assembly of luminescent rare earth hybrid materials.

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Fig. 2. Scheme for synthesis of ternary rare earth hybrid Eu/Tb–(PHA-Si)–PMMA and the predicted composition of the

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corresponding materials (Reprinted with permission from Ref. 32. Copyright 2010, Elsevier Publishing Company)

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Fig. 3. The predicted composition of the ternary rare earth hybrids RE-BFPP-Si-PEG (Reprinted with permission from

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Ref. 37. Copyright 2010, Springer Nature Publishing Company)

Fig. 4. The synthetic scheme and predicted structure of covalent assembled ternary MCM-41 / poly(ionic liquid) / rare earth complexes hybrid materials, and the photograph of the resulted materials under daylight (top) and 360 nm UV Lamp (bottom) (Reprinted with permission from Ref. 53. Copyright 2018, MDPI Publishing Company)

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Fig. 5. Preparation scheme of hybrid materials LnW10-IM-[ZA/L*Eu-TTA] and LnW10-IM-[ZA/L*Tb-TAA] (Ln = Eu, Tb, Sm or Dy) (Reprinted with permission from Ref. 64. Copyright 2015, Royal Society of Chemistry Publishing

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Fig. 6. Scheme for preparation of ternary hybrid ZnO-MAA-HEMA-RE-phen (b) and its predicted composition (Reprinted with permission from Ref. 70. Copyright 2012, Royal Society of Chemistry Publishing Company)

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Fig. 7. The synthesis process for multifunctional rare earth hybrids MMS·Im +·[Eu(β-diketonate)4]– (Reprinted with

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permission from Ref. 83. Copyright 2013, John Wiley and Sons Publishing Company)

Fig. 8. The scheme to assemble white light LED with In-MOF-Eu hybrid; The emission spectra and CIE diagram for the LED lamp under different excitation wavelength (Reprinted with permission from Ref. 101. Copyright 2016, Royal Society of Chemistry Publishing Company)

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Fig. 9. Schematic of the procedure for the preparation of photo-catalytic hybrid MIL-125(Ti)@TiO2 and

multi-component luminescent [email protected](Ti)@TiO2 (Reprinted with permission from Ref. 106. Copyright 2018,

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Fig. 10. Scheme for the preparation of quaternary hybrid materials Ln-SBA-15-Si-IRMOF-3 (Ln = Eu, Tb, Nd, and Yb) (Reprinted with permission from Ref. 108. Copyright 2015, Royal Society of Chemistry Publishing Company)

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The viable assembly units of multi-component assembly of luminescent rare earth hybrid materials are reviewed