Synthesis,Structure And Properties Of Metallic Bond Diruthenium Compounds With Paddlewheel And ESBO Configuration

In recent years,there are many compounds based on diruthenium units,most of which focus on the structural determination and magnetic study of crystal compounds.There is no related report on the effect of intercalated structure on the structure and magnetism of the compounds.Therefore,it is very challenging to prepare intercalated structure compounds with a tunable number of lattice molecules.In the aspect of magnet construction,the effects of particle size effects and defects on magnetic properties have not been deeply studied.In this paper,the coordination assembly of Ru-Ru metal multiple bonds with two kinds of configurations was studied,and the layered compounds with tunable number of lattice water insertion were successfully prepared,and the effect of lattice water insertion on magnetism was discussed.The magnetic effect of sample defects was explored by grinding treatment.And the configuration transformation of Paddlewheel-ESBO was successfully realized by using N heterocyclic ligands.The main research results of this paper are as follows:1.Construction of four Paddlewheel-type compounds 1-4,and the exploration of the size effect on the magnetic properties of compounds 3,5-7Firstly,heterometallic phosphates neutral layer{Mn（H₂O）₄}₂Mn（H₂O）₂Ru₂（PO₄）₄（H₂O）₂（A）constructed by Ru₂（HPO₄）₄^3-and Mn²⁺.Alkaline strength plays a crucial role in directing a different number of lattice water-intercalated structures.In the presence of CH₃COO₂^-and SO₄^2-as assisting reactants,the assembling reaction in aqueous solution resulted in compounds A·10H₂O（1）and known compounds A·4H₂O,respectively.The neutral heterometallic phosphate layers of A are separated by a different number of interlayer lattice water molecules,and hydrogen bonds are responsible for the connection of adjacent neutral layers.Magnetism measurements combined with structural analysis show that compound A·10H₂O exhibits soft magnet behaviour below 8.5 K by connecting adjacent ferrimagnetic layers through indirect hydrogen bonding,and a reentrant spin-glass-like transition is observed for compound A·4H₂O,exhibiting two steps transition at 8 and 12 K,due to a strong competition between intralayer magnetic coupling and interlayer antiferromagnetic interactions mediated through the direct hydrogen bonding.Therefore,it is successfully confirmed that the type of anion is a major factor influencing the construction of the compound.Secondly,M（CH₃CO₂）₂（M=Mg,Ni）and Ru₂（HPO₄）₄^3-self-assembled in a 2D compound[{Mg（H₂O）₄}₂Mn（H₂O）₂HRu₂（PO₄）₄（H₂O）₂]·10H₂O（2）and 1D chain compound H[Ru₂（PO₄）₄（H₂O）₂][Ni（H₂O）₅]₂[Ni（H₂O）₂]·6H₂O（3）.Compound2 is isomorphic to compound 1,compound 3 exhibits the characteristics of a spin glass.Finally,it was also found that when the temperature was adjusted to below 273.15 K,a 2D layered compound K_2.5H_2.5Ru₂（PO₄）₄（H₂O）₂Mn（H₂O）₂·3H₂O（4）was obtained using transition metal salts of anions such as SO₄^2-,and the magnetic analysis showed a weak ferromagnetic interaction between the diruthenium unit of compound 4 and Mn²⁺.Four ferromagnetic compounds 3 and 5-7 were selected for grinding,and the effect of particle size on magnetic properties was studied by magnetic testing.The results showed that the magnetic hardness of the samples could be greatly improved after a certain degree of damage treatment.2.Construction of two ESBO compounds 8-9Ru₂（CO₃）₄^3-reacted with two piperazine ligands at a certain molar ratio,alkaline hydrolysis in aqueous solution successfully achieved the transformation of the configuration,two ESBO-type compounds were assembled,Ru₂O₂（CO₃）₂（H₂O）₂(C₆H₁₂N₂)₂·12H₂O（8）,Ru₂O₂（CO₃）₂（H₂O）₂(C₅H₁₁N₂)₂·4H₂O（9）,respectively.The above two compounds were characterized.