Multi-Nuclear Rare-Earth-Implanted Tartaric Acid-Functionalized Selenotungstates and Their Fluorescent and Magnetic Properties

Abstract

A family of multinuclear rare-earth (RE)-implanted H2tart2–-functionalized selenotungstates (STs) [H2N­(CH3)2]13H­{[W2O5(OH)2­(H2tart)2]­(H2tart)­{[W3O6RE2­(H2O)6]­[SeW9O33]2}2}·31H2O [RE = Eu3+ (1), Tb3+ (2), Dy3+ (3), Ho3+ (4), Y3+ (5); H4tart = d-tartaric acid] have been afforded by a simple one-pot aqueous reaction and were structurally characterized. Intriguingly, their isomorphous organic–inorganic hybrid anion {[W2O5(OH)2­(H2tart)2]­(H2tart)­{[W3O6RE2­(H2O)6]­[SeW9O33]2}2}14– includes two sandwich-type {[W3O6[RE2(H2O)6]­[SeW9O33]2}4– dimeric units with a W–O–RE heterometal core, which are further joined by two H2tart2–-decorated dinuclear tungsten-oxo {W2O5(OH)2(H2tart)2} clusters and a bridging H2tart2– ligand, contributing to a surprising Mobius band-like configuration. It is worth emphasizing that three H2tart2– ligands coordinate with tungsten centers rather than RE cations. For all we know, 1–5 delegate the infrequent RE-implanted STs functionalized by triplicate H2tart2– bridges. Furthermore, fluorescent performances of 1–4 as well as magnetic properties of 2–4 have been surveyed. The solid-state fluorescence emission spectra prove that each of them undoubtedly shows the characteristic emission peaks of RE cores, while alternating-current susceptibility measurements suggest field-induced single-molecule magnetic behavior in 3.

Two Types of Subgroup-Valence Heteroatoms (PIII, TeIV) Synergistically Controlling Octa-CeIII-Encapsulated Heteropolyoxotungstate and Its Electrochemical Recognition Properties

“…), which can further generate multitudinous lacunary and versatile HPOT building blocks (BBs) to render them as connection nodes to capture rare-earth (RE) or transition-metal (TM) ions. − Among the diverse heteroatoms, the lower valence state and lone electron pair effect of subgroup-valence heteroatoms (SVHAs) with triangular pyramidal coordination configuration (As III , Sb III , Te IV , Se IV , etc.) can more easily motivate the generation of multiple defect HPOT BBs, which can be trusted to obtain distinguished HPOT aggregates having unpredictable structural features and performances. − For instance, the triangular pyramidal TeO 3 2– as the SVHA source can bear three bonds together with three oxygen atoms, leading to partially enclosed or open HPOT clusters that can further be linked by metal ions (TM or RE) into gigantic structures. , …”

An Inorganic Pac‐Man: Synthesis, structure and electrochemical studies of a heterometallic {YCoII3W} cluster sandwiched by two germanotungstates

“…Lacunary POMs as multidentate O‐donor ligands have a good affinity for various electrophiles, such as transition metal (TM) [11] or rare earth (RE) centers [12] to generate diverse structures with interesting properties. Among the multitude of RE‐containing POMs, Y III embedded POMs are very limited [13–18] …”

Construction of novel hexanuclear Co(II) and dinuclear Ni(II) bis(salamo)‐type complexes

“…[1][2][3][4] It is found that some factors such as the types of metal salts and ligand structures may affect the construction of "multidecker" complexes. There has been considerable interest in multinuclear selfassemblies [5][6][7][8] designed and synthesized by transition metal ions and organic ligands. [9][10][11][12][13][14] In addition, the general strategy for designing multinuclear complexes is to use ligands in two coordination environments, which may exhibit different coordination modes with metals.…”