Synthesis,Structures And Magnetic Properties Of Heterometallic Diruthenium Phosphates Based On The Protonated Ru₂?PO₄?₄^n- Unit

In recent years,molecular materials containing Ru-Ru metal bond have developed rapidly in the field of material chemistry.The construction of molecular-based magnets based on Ru₂^4/5+has received great attention.The binuclear ruthenium unit bridges and chelates with some acid ligands?carboxylate,carbonate,phosphate,sulfate,etc.?to form a ligand unit with paddle structure.By reacting with some rare earth metals and transition metal ions,it can form multiple mixed metal compounds with different structure and novel magnetic properties.Due to their special magnetic properties,these compounds are widely used in various fields,including small molecule devices,catalysis,medicine,memory magnetic devices,etc.It has aroused more and more interest of scientists in different fields.This paper uses mixed-valence protonated ruthenium phosphate Ru₂?HPO₄?₄^3-as the building block.It reacts with alkali metals,alkaline earth metals and transition metal salts in the presence of template agents such as hydrogen peroxide and organic amine which can obtain eighteen new compounds based on Ru-Ru metal multiple bonds.The structures were measured by single crystal x-ray diffraction,and the magnetic properties of the compounds were studied.1. Ru₂?HPO₄?₄^3-self-assembled with the metal iron Mg/Ni/Zn/Co forming ionic crystal compounds 1-11In this chapter,mixed-valence protonated H₃Ru₂?HPO₄?₄is used as the building unit by adding hydrogen peroxide and 1-methylpiperazine solution reacting with Co²⁺to obtain complex?C₄N₂H₆?{Co?H₂O?₆}[Ru₂?PO₄?₄?H₂O?₂]·4H₂O?1?.H₃Ru₂?HPO₄?₄adds hydrogen peroxide and N,N'-diethylpiperazine reacting with Co²⁺to obtain(C₈N₂H₁₄){Co?H₂O?₁₀}[Ru₂?PO₄?₄?H₂O?₂]·5H₂O?2?.Adding hydrogen peroxide and ?C₄N₂H₆?{Co?H₂O?₆}[Ru₂?PO₄?₄?H₂O?₂]·5H₂O?3?.H₃Ru₂?HPO₄?₄mixs with hydrogen peroxide and 2-methylpiperazine solution reacting with Ni²⁺and we can get complex?C₄N₂H₆?{Ni?H₂O?₆}[Ru₂?PO₄?₄?H₂O?₂]·6H₂O?4?.Compounds 1,2,3,and 4 all contain the binuclear ruthenium phosphate unit of the same state,with organic amine cations and metal ions containing coordination water{M?H₂O?_n}²⁺[M=Co/Ni;N=6/10].We can synthesize compound?NH₄?₂[{Mg?H₂O?₅}₂Ru₂?PO₄?₄?H₂O?₂]·4H₂O?5?by adding hydrogen peroxide and NH₃·H₂O with Mg²⁺.The oxidized state binuclear ruthenium phosphate unit and two{Mg?H₂O?₅}²⁺are inter-connected to form ionic compound.Protonated ruthenium phosphate reacts with 1-methylpiperazine and Mg²⁺/Ni²⁺/Co²⁺obtain isomeric compounds?C₅N₂H₇?{M?H₂O?₆}[Ru₂?PO₄?₄?H₂O?₂]·6H₂O[M=Mg?6?;M=Ni?7?;M=Co?8?],which consist of mixed valence binuclear ruthenium phosphate units and free hex-acoordinated ?NH₄?[{M?H₂O?₅}₂Ru₂?HPO₄?₂?PO₄?₂?H₂O?₂]·4H₂O[M=Mg?9?;M=Zn?10?;M=Ni?11?].The mixed valence binuclear ruthenium phosphate unit connects two M?H₂O?₅²⁺to form a C-configuration heterometallic ruthenium phosphate series compounds.2. Ru₂?HPO₄?₄^3-self-assembled with the metal iron Zn/Co/Cu/Ni forming one-dimensional coordination compound 12-16Using mixed valence protonated H₃Ru₂?HPO₄?₄as raw material,adding N,N'-dimethylpiperazine solution reacts with Zn²⁺to obtain compound?C₆N₂H₈?₂Zn[Ru₂?PO₄?₄?H₂O?₂]₂·4H₂O?12?.It is formed by four-coordinated Zn²⁺connecting adjacent binuclear ruthenium phosphate units attaining chain structure.Reaction with Co²⁺yields the compound H{Co₂?H₂O?₇}[Ru₂?HPO₄?₂?PO₄?₂?H₂O?₂]·6H₂O?13?.The structure contains two different coordination modes of Co²⁺that connects adjacent dinuclear ruthenium phosphate units to forming one dimensional chain.Adding piperazine and Cu²⁺gets compound H₂?C₄N₂H₆?₃[Ru₂?PO₄?₄?H₂O?₂]_2·5H₂O?14?.H₃Ru₂?HPO₄?₄reacts with N,?C₆N₂H₆?{M?H₂O?₆}₃[Ru₂?PO₄?₄?H₂O?₂]₂·4H₂O[M=Ni?15?;M=Co?16?].The adjacent two binuclear ruthenium phosphate units in compounds 14,15 and 16 are connected to each other through oxygen of one phosphate and oxygen from the water molecule to form a one-dimensional chain structure.3. Ru₂?HPO₄?₄^3-self-assembled with CdSO₄forming two-dimensional layered coordination compound 17Self-assembly reaction of mixed valence H₃Ru₂?HPO₄?₄and CdSO₄in aqueous solution yields two-dimensional layered coordination compound H₃[Cd₂?H₂O?₄][Ru₂?PO₄?₄?H₂O?₂]·4H₂O?17?.There is a Cd-O-Cd-O four-ring structure in the compound and a two-dimensional layered structure is formed by inter-connecting the four rings with the mixed-valence binuclear ruthenium phosphate unit.The compound exhibits antiferromagnetic behavior.4. Ru₂?HPO₄?₄^3-self-assembled with ZnSO₄to form a three-dimensional framework structure coordination compound 18The mixed valence Ru₂?HPO₄?₄^3-reacts with ZnSO₄solution,adding ammonia to adjust p H=3.5,and finally we obtains a three-dimensional framework structure coordination compound?NH₄?₂{Zn₃?H₂O?₇}[Ru₂?HPO₄?₂?PO₄?₂?H₂O?₂]₂·4H₂O?18?.Compound 18 forms a three-dimensional structure by connecting Zn²⁺with three different coordination modes to the bivalent ruthenium phosphate of in three directions of abc.The compound shows antiferromagnetic behavior.