Recent advances in lanthanide-based POMs for photoluminescent applications

Abstract

Since the the first formation of the famous "Peacock-Weakley" anions [Ln(W5O18)2]8/9-, a steady stream of breakthroughs have been made in the chemistry of multitalented lanthanide (Ln)-based polyoxometalates (POMs) for their...

Photocatalytic Reduction of Nitrobenzene to Aniline by an Intriguing {Ru(C6H6)}-Based Heteropolytungstate

“…Polyoxometalates (POMs) are a specific family of nanosized anionic metal–oxygen clusters of defined composition and structure, consisting of classical transition metal ions (Mo, W, V, Nb, and Ta) with oxygen atoms, emerging as a new functional material with a broad range of applications in medicine, synthetic chemistry, and catalysis. − In recent years, POM-based photocatalysts have been in the limelight because of their excellent redox ability and powerful electronic storage capability but accompanied by the problem of poor light utilization efficiency, difficult recycling, and poor chemical selectivity − ; thereby, it is necessary to develop more efficient POM-based derived materials. The introduction of transition metals (TMs) into POMs not only improved the photocatalytic efficiency but also extended the absorption spectrum of these metal–oxygen clusters into the visible range .…”

Synthesis and Characterization of 6-Ti-Substituted Polyoxomolybdate with High Catalytic Activity for Sulfide Oxidation

“…Polyoxometalates (POMs) are composed of {MO x } polyhedral building blocks, in which M represents group V and VI elements (Nb, Mo, W, Ta, V) in their highest oxidation state. , Due to their adjustable acidity, redox capabilities, and high stability, POMs have been extensively investigated across various domains, including biological medicine, materials science, magnetism, catalysis, etc. − Transition-metal-substituted POMs (TMSPs) are a crucial branch of POMs, which have attracted extensive research interests for their diverse structures and excellent properties. − Notably, the study of TMSPs has mainly focused on manganese, iron, cobalt, nickel, copper, and zinc substitutions, resulting in the establishment of several compelling structures. − Titanium-substituted POMs (TiSPs) exhibit distinctive structural and functional properties compared to other transition-metal-substituted POMs, indicating their potential utility in catalysis, photoelectric chemistry, and energy conversion. − The substitution of M atoms with Ti atoms in POMs is particularly intriguing as it allows the creation of polycentric active centers through corner- or edge-sharing {TiO 6 } octahedra and facilitates the formation of multimers via Ti–O–Ti bonds. However, despite these promising characteristics, the development of TiSPs lags behind that of other TMSPs …”

Effect of Ligands on Quantum Tunneling of Magnetization for Dysprosium C4v Single-Molecule Magnets with Theoretical Insights

“…The unveiling of single-molecule magnet (SMM) behavior in the [Mn 12 ] cluster has greatly intrigued a vast array of chemists and materials scientists. , Particularly, SMMs with high performance show potential applications in various fields. − After early domination by 3d transition metal (TM) ion in SMMs, the field has seen a significant emergence of Ln-based SMMs since the first synthesis of [Tb­(Pc) 2 ] − in 2003. − Compared with TM ions, lanthanide ions possess an intrinsically high uniaxial anisotropy due to their unquenched orbital momentum and strong spin–orbit coupling. This feature makes them highly advantageous for enhancing the SMM performance, evidenced by high energy barrier ( U eff ) and blocking temperature ( T B ). − The mononuclear Ln III -based SMMs are proved to bear unexpected records of high U eff and T B owing to their strong spin–orbit coupling, the absence of complex internal exchange in the compound, and the inherent anisotropy of spin carriers. , Meanwhile, their simple composition of individual metal ions makes them easily designable and controllable, which allows for easily understanding the anisotropy, crystal-field environment, and relaxation dynamics behavior of intricate lanthanide ions .…”