Synthesis,Structures And Properties Of Lanthanide Clusters And Lanthanide-Transition Metal Clusters

Lanthanide/lanthanide-transition metal hydroxide cluster complexes,with an unmatched range of physical and chemical properties,have become a focus of interest in recent decades for their fascinating structures and variety of specific applications including single molecule magnets,molecular magnetic coolers and so on.More importantly,investigations in this field are regard as filling the gap between the quantum and classical worlds of nanoscale compounds.The development of such fascinating compounds is subject to the limitation of synthetic challenges.At present,reasearchers usually synthesize polynuclear lanthanide/lanthanide-transition metal hydroxide cluster complexes via solution method.Herein,we obtain one 3D heptanuclear lanthanide cluster?compound 1?,five monodisperse 48-core lanthanide clusters?compounds 2-5?,two 3D lanthanide-transition metal hydroxide cluster complexes?compounds 6-7?,one lanthanide-organic complex?compound 8?and one tetranuclear titanium-organic complex?compound 9?via hydro/solvothermal method.A 3D heptanuclear lanthanide cluster,namely La₂??₃-O??dcd?₂?1?,were hydrothemally synthesized from lanthanide metal La and 3,3-dimethyl-1,2-ciprofloxacin acid?H₂dcd?ligand.Compound 1 crystallizes in the trigonal space group R3^<sub>.Compound 1is a 3D network constructed by six-core lanthanide clusters and six La³⁺ions branch out,besides,each La³⁺link with six[La₆]clusters.We synthesize a series of high-nuclearity48-core lanthanide clusters Ln₄₈O₃₂?3,4-pdda?₁₈?dmpa?₁₄Br₂·14H₂O[Ln=Gd?2?,Eu?3?,Tb?4?,Dy?5?],by employing the 2,2-Bis?hydroxymethyl?propionic acid?H₂dmpa?,3,4-pyridinedicarboxylic acid?3,4-pddaH₂?and rare earth nitrates.These monodisperse polynuclear lanthanide hydroxide clusters are structurally analogous,the packing of 48lanthanide atoms exhibit a drum-like structure.In addition,aspects of the fluorescence properties of compounds 3 and 4 are discussed.The use of iminodiacetic acid?H₂ida?,tetrazol-1-yl-acetic acid,samarium oxideor europium oxide has led two unprecedented 3-D lanthanide-transition metal coordination polymers[Ln₂₀Co₂₄?Hida?₁₂?ida?₁₅(C₈O₇N₂H₁₀)₃?OCH₂CH₃?₃?CO₃?₆?C₂O₄?₃??₃-OH?₂₁-??2-OH?3]?OH?15·80H2O[Ln=Sm?6?,Eu?7?].Compounds 6 and 7 are structurally analogous,they are 3D networks which are linked by 41-core lanthanide-transition metal hydroxide clusters[Ln₂₀Co₂₁]and six Co?Hida?₂ branch out.Notably,they present 1-D chanels along the c-axis.Proton-conducting and gas storage properties are also disscussed in this thesis.The reaction of Nd₂O₃ and Al?OH?₃ with iminodiacetic Acid in EtOH solution led to a novel 3D lanthanide-organic complex Nd2?ida?3?H2O?2?8?.Compound 8 crystallizes in the tetragonal space group I4₁/a.The structure of compound 8 can be regard as the result of the packing of 14-core rings.A monodisperse titanium-organic compound named[Ti₄?Hdmpa?₄?OCH₃?₄?H₂O?₂]?OH?₄?9?,have been obtained by using titanium isopropoxide,2,2-Bis?hydroxymethyl?propionic acid and anhydrous methanol.Compound9 crystallizes in the trigonal space group R3^<sub>.Titanium atom connect with main ligand?dmpa?,auxiliary ligand?OCH₃?and H₂O.The work of this paper enriches the contents of synthetic and structural chemistry in lanthanide/lanthanide-transition metal hydroxide cluster complexes,and opens up a new path to prepare functional lanthanide/lanthanide-transition metal clusters materials,which are of significance to the exploitation of this field.