Synthesis, Structure And Magnetic Properties Of M-Ru2, Ln-Ru2 Type Mixed Metal Dinuclear Ruthenium Phosphate Compounds

Inorganic acid anions with high negative charge,such as CO32-,PO43-and SO42-,can chelate and bridge Ru-Ru metal-metal bonds forming paddle wheel unit,and exibit some unique magnetic properties.So far,carbonate diruthenium units linked by transition metal and rare earth ions forming M-Ru2 and Ln-Ru2 hetorometallic carbonates have studied extensively,and these compounds show different properties such as weak ferromagnetic,ferrimagnetic,metamagnetic and spin glassy properties.In this paper,an investigation of halogen Cl-influence on the self-assembling Ru2(PO4)47-paddle-wheel precursors Co2+and Cu2+ ions in aqueous solution has resulted in three novel 3d-4d heterometallic phosphates.Mixed-valent Ru2(PO4)4-paddle-wheel precursors reaction with Ln3+ has resulted in five 4d-4f heterometallic phosphate chain compounds.While homo-valent cu2(PO4)46-units linked by rare earth ions resulted in four 2D layered compounds and one 3D compound.The contents include three parts as follows:1.M-Ru2(II,III)3d-4d heterometallic phosphonates[Cu(H20)2]2Cu(H20)4HRu2(P04)4(H20)2·2H2O(1);[Cu(H2O)]8H10{[Ru2(PO4)4]4Cl6}·19H20(2),[Li(H20)4]2[Co(H20)4]2[Co(H20)2]H[Ru2(P04)4Cl2].4H20(3).Compound 1 shows metamagnetic properties,and compound 3 exhibits spin canting behavior.2.Ln-Ru2(II,III)4d-4f heterometallic phosphonatesIn different pH value condition,a series of heterometallic phosphonates have been obtained:[Ln(H20)4]H2[Ru2(P04)4(H20)2]·6H2O {Ln = La(4),Ce(5),Pr(6),Nd(7),Sm(8),Eu(9),Tb(11),Dy(12)}.These compounds showing a chain structure and the single-crystal structures of 8-12 have been determined.All of them show antiferromagnetic interaction between paramagnetic center ions.3.Ln-Ru2(?,?)4d-4f heterometallic phosphonatesHomo-valent Ru2(PO4)46-units linked by rare earth ions resulted in four 2D structural compounds[Sm(H20)4]2H[Ru2(P04)4(H20)2]·4H20(13),[Eu(H20)4]2H[Ru2(P04)4(H2O)2]·4H20(14),[Tb(H2O)3]2H[Ru2(PO4)4(H20)2]·8H20(15)and[Dy(H2O)3]2H[Ru2(PO4)4(H2O)2]·8H2O(16).While Ru2(PO4)46-reaction with Gd3+ a novel 3D compound Gd(H2O)3]2 H[Ru2(PO4)4(H2O)2]·4H2O(17)has been obtained.And these compounds(13)-(17)show antiferromagnetic interaction between paramagnetic centers.