Self‐Assembly of Nanometer‐Scale [Cu₂₄I₁₀L₁₂]¹⁴⁺ Cages and Ball‐Shaped Keggin Clusters into a (4,12)‐Connected 3D Framework with Photoluminescent and Electrochemical Properties

Abstract

The design and construction of coordination polymers from preformed metal clusters, [1] such as metal carboxylate clusters [2] and chalcogenide supertetrahedral clusters, [3] to produce new materials with unique properties have been the focus of recent research interest. However, given the importance of cuprous iodide clusters in photochemistry and photophysics, [4] as well as their considerable variety of structural forms not encountered for other iodometalates, [5] it is surprising that relatively little progress has been made in using them as building blocks for the fabrication of multidimensional coordination frameworks.[6] On the other hand, polyoxometalates (POMs), [7,8] as a unique class of metaloxide clusters, have many properties that make them attractive for applications in catalysis, biology, magnetism, optics, and medicine.[9] Impressive studies on linking of these welldefined metal-oxygen building blocks to generate giant discrete clusters and related extended structures have been performed. [10,11] However, up to now no reports have been made on the combination of these two interesting fields to prepare high-dimensional cluster-based compounds, although POM chemistry has touched an almost unprecedented number of other fields of chemistry.[9b] Such composite materials present the opportunity to generate high-dimensional nanoscopic assemblies from even larger multinanounits and also have vast potential for use in materials science by incorporation of their own physical and chemical properties.Among the many different types of POMs, we chose the Keggin heteropolyanions, as they are the most widely recognized and thoroughly studied. Furthermore, we used the N-heterocyclic ligand 4-[3-(1H-1,2,4-triazol-1-yl)propyl]-4H-1,2,4-triazole (L, see the Supporting Information) for our synthetic strategy because 1) its clawlike donor atoms and bent coordination geometry offer the possibility of incorporating more metal atoms into high-nuclearity clusters, and 2) ligands containing a large number of N atoms could partially reduce Mo VI to Mo V , [12] whereby the surface charge density of the polyanion is increased and the surface oxygen atoms are activated to facilitate formation of high-dimensional covalent networks. Herein we report the synthesis, structure, and luminescent and electrochemical properties of an unprecedented (4,12)-connected 3D network, namely, (NH 4

An unprecedented (3,4,24)-connected heteropolyoxozincate organic framework as heterogeneous crystalline Lewis acid catalyst for biodiesel production

“…So far, only three topologies combine 4,12-connected components in the RCSR database, that is, ith , shp , and ftw . Notably, our group has reported a (4,12)-connected ith topology network (Figure S7)53.…”

Self‐Assembly of Hierarchical Nanostructures from Dopamine and Polyoxometalate for Oral Drug Delivery

“…Several methods have been reported for delivering drugs to specific target tissues in the body. [18] Among these, utilization of pH changes within the gastrointestinal (GI) tract is of special interest in the design of oral delivery protocols for drugs, since a marked pH change occurs along the GI tract from acidic in the stomach (pH 1-3) to basic in the intestine (pH [5][6][7][8]. [19] In the present work, release of the drug from the hierarchical nanostructures was studied at two pH values of 2.8 and 7.4, as shown in Figure 6 e. The release of doxorubicin was found to be pH-dependent.…”

“…[5] On the other hand, polyoxometalates (POMs), a well-known class of metal-oxide nanoclusters, are frequently used as suitable inorganic building blocks for the construction of hybrid materials owing to their controllable size, shape, and high negative charges, as well as their diverse electronic, magnetic, photochemical, and catalytic properties. [6] Impressive studies have been conducted on the co-assembly of biomolecules and polyoxoanions to generate functional organic-inorganic hybrid materials. [7] However, to the best of our knowledge, there has been no report on the combination of bioactive components and POMs to fabricate 3D hierarchical nanostructures with multiple functions.…”

Photocatalytic Performance of H6P2W18O62/TiO2 Nanocomposite Encapsulated into Beta Zeolite under UV Irradiation in the Degradation of Methyl Orange

“…Polyoxometalates are classes of well‐defined metal‐oxygen clusters which have attracted much attention due to their interesting variety of architectures making them as potential materials for different applications. They have been used in various fields including catalysis, magnetism, sorption, biomedicine, fuel cell, membrane, material science and photochemistry . In addition, they have been selected as catalysts for their availability, their proper size to incorporate to support cage and acid safety comparing with mineral acids.…”