A 3D mixed-valence Co（Ⅲ）-Co（Ⅱ） compound [Co9（bta）10（Hbta）2（H2O）10]n·[22（H2O）]n （1） （H2bta=N,N-bis（1H-tetrazole-5- yl）-amine） was hydrothermally synthesized by reaction of Co（NO3）2·6H2O with H2bta·H2O. Compound 1 consists of three kinds of distorted-octahedral [CoⅡ（N4O2）] paramagnetic nodes which are separated by [CoⅢ（bta）2（Hbta）]2-/[CoⅢ（bta）3]3- dia- magnetic linkers to generate a 3D porous metal-organic framework （MOF） with alternative …Co（Ⅲ）…Co（II）… array and channels incorporating water molecules. Under an applied magnetic field of 4000 Oe, compound 1 exhibits slow relaxation of magnetization at low temperatures, giving AE/kB=30.O0 K and ι0=2.0×10^-8 s.
Three new heterometallic coordination compounds, namely, [KCu（I3）（L）2（H2O）2]n （1）, [KCu（I3）（L）2（H20）]n （2） and [CIIK4（I3）z（L＇）4]n （3）, were prepared and characterized （HL=5-methylpyrazine-2-carboxylic acid, HL＇=p-tolylacetic acid）. Structural studies revealed that 1 and 2 exhibit 3D frameworks with rectangular channels occupied by triiodide ions. Both compounds can be symbolized as a 5-connected net with pcu topology. In compound 3, a one-dimensional polyhedral chain is connected by hexanuclear mask like clusters [Cu2K408]. These chains are further linked each other via rare （1,1,3,3）-triiodide ion-bridging units to generate a 3D （4,5,6）-connected net with the point symbol of { 12}2{4·12^2}4{4^6}{4^8·62}4{49.66}4. It is noteworthy that water-induced reversible dissolution/reorganization processes occur between 1/2 and [Cu（L）2（HzO）],＇3nH20. The thermal and photoluminescence properties of compounds 1, 2, and 3 were investigated as well.
