Preparation of a Lanthanide–Titanium Oxo Cluster–Polymer Composite by Cu^I‐Catalyzed Click Chemistry

Abstract

Incorporating metal clusters within the skeleton of the organic polymers through a click reaction cannot only effectively prepare cluster–polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide‐containing lanthanide–titanium oxo cluster of Eu8Ti10‐N3 (Eu8Ti10‐N3=[Eu8Ti10(μ3‐O)14(H2O)4(OAc)2(tbba)30(paza)4(THF)2]⋅4 THF⋅8 H2O (1), Htbba=4‐tert‐butylbenzoic acid, Hpaza=4‐azidobenzoate, HOAc=acetic acid, THF=tetrahydrofuran) through an in situ solvothermal reaction of 4‐azidobenzoic acid and 4‐tert‐butylbenzoic acid. Reaction of 1 with PEG (PEG=methoxypoly(ethyleneglycol)alkyne, 2000 g mol−1) through CuI‐catalyzed click chemistry generates a lanthanide–polymer composite of Eu8Ti10‐N3@PEG (2). Investigation with IR, 1H NMR and ICP‐OES of 2 indicates that the structural integrity of 1 is maintained in 2. Study of the luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically remains unchanged in 2. Significantly, the formation of 2 cannot only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster–polymer composite luminescent materials.

Cross-Linked Luminescent Polymers Based on β-Diketone-Modified Polysiloxanes and Organoeuropiumsiloxanes

“…There are some routes for obtaining luminescent materials, namely, the incorporation of luminophores into a polymeric matrix, either organic fluorescent dyes [16][17][18][19] or inorganic dyes, such as quantum dots [20,21], nanoparticles [22][23][24], lanthanide salts [25], MOFs [26], and complex compounds [27][28][29][30]. Luminophores can be covalently bonded to a matrix [31,32] or used as fillers [20,21,23,24,26,28]. Such polymer materials are mainly supposed to be utilized as light-emitting diodes (OLEDs) [18,20,23], including white OLEDs [21,29], but also as luminescent coatings [26], chemosensors [19], and upconverting composite materials [24].…”

A lanthanide-titanium oxo cluster-polymer composite: From clusters to fluorescent ink

“…However, the poor solubility and film-forming properties of LTOCs make them difficult to use directly as fluorescent inks. In previous work, we have demonstrated that the preparation of LTOCpolymer composites (LTOCPs) through covalently link-ing LTOCs to polymers can effectively improve the mechanical properties of the LTOCs, without noticeably changing their luminescent performance [29] (0.08 mmol, 24 µL). The purity of bulk sample 1 was demonstrated by the similarity between experimental powder X-ray diffraction (PXRD) patterns and simulated patterns (Fig.…”