Syntheses, structures, luminescence and magnetic properties of three high-nuclearity neodymium compounds based on mixed sulfonylcalix[4]arene-phosphonate ligands

Abstract

The solvothermal reactions of p-tert-butylsulfonylcalix[4]arene (H4BSC4A), phosphonic acid and neodymium chloride have resulted in three novel high-nuclearity neodymium coordination compounds.

Luminescent Lanthanoid Calixarene Complexes and Materials

“…An elegant recent example reports a series of Nd clusters, supported by p -tert-butylsulfonylcalix[4]arene and phosphonate co-ligands. Nd 10 , Nd 11 , and Nd 19 clusters were isolated and structurally characterised, depending on the specific phosphonate coligand used, and the stoichiometry [ 51 ]. Upon excitation at 375 nm, the emission spectra of all three clusters exhibited the near IR characteristic bands of the Nd(III) ion ( Figure 10 ).…”

“… Near Infrared (NIR) luminescence spectra of the Nd 10 , Nd 11 , and Nd 19 clusters supported by p -tert-butylsulfonylcalix[4]arene in the solid state at room temperature. Reproduced by permission of The Royal Society of Chemistry from [ 51 ]. …”

Ligand Induced Double-Chair Conformation Ln12 Nanoclusters Showing Multifunctional Magnetic and Proton Conductive Properties

“…In the past decades, people have reported many lanthanide clusters with different nuclear numbers. − Meanwhile, structures with various shapes and conformations are discovered, such as wheel, tube, disk, core–shell, and other atypical conformations. − This is very conducive for better understanding the cluster assembly mechanism and designing lanthanide clusters in the future. The construction of metal nanoclusters is usually affected by external factors during the preparation processes. − In general, to modulate structural conformations, one can screen the reaction conditions, for example, the ratio of metal and ligand, pH conditions, anion template, and so on. − However, these methods are often fussy. In comparison, modifying organic ligands can change the coordination modes directly, which will be a powerful means to regulate the conformations of nanoclusters. − For example, by using similar ligands, a series of Ln 12 clusters with different conformations were obtained, although these compounds share the same number of nuclei.…”

Impact of flexible succinate connectors on the formation of tetrasulfonylcalix[4]arene based nano-sized polynuclear cages: structural diversity and induced chirality study

“…Among the accessible metacyclophanes, one should mention the calix[4]arene 11 (1-4H, figure 1) and, especially, thiacalix[4]arene 12 (2-4H, figure 1) as well as tetrasulfonylcalix[4]arene 13,14 (3-4H, figure 1) based polydentate macrocyclic ligands, owing to the preorganized orientation of the coordinating sites, when adopting their cone conformation. They possess the fascinating ability to form various polynuclear homo-and heterometallic clusters when coordinated to d/f metal cations 15,16,17,18,19 exhibiting attractive luminescence properties 20,21,22,23,24,25,26 and magnetic behavior. 27,28,29,30,31,32,33,34 Also using 1-4H and 2-4H in cone conformation as a building species, the formation of extended coordination networks in the crystalline phase was extensively documented.…”