Koordinationspolymere mit Tris(4‐carboxyphenyl)‐phosphanoxid als Ligand – Synthese,Kristallstrukturen und topologische Untersuchungen

The solvothermal reaction of MnCl₂ · 4H₂O or CoCl₂ · 6H₂O with tris(4‐carboxyphenyl)‐phosphine oxide (H₃TPO), in DMF orDMA resulted in the four coordination polymers M₃(tpo)₂(dmf)(H₂O)₂]( 1 : M = Mn; 2 : M = Co), (NMe₂H₂)Mn₃Cl(HCO₂)(htpo)(tpo)(H₂O)] ( 3 ) and (NMe₂H₂)Mn₃(tpo)₂(OAc)] ( 4 ). Structural characterization by X‐ray crystallography revealed that 1 – 4 form 3‐periodical infinite networks; after synthesis solvent molecules occupy the framework pores. The topologies of the networks in 1 , 2 and 3 are unprecedented in literature and are systematically characterized. Furthermore, these topologies could be derived from hexagonal close packing ( 1 , 2 ) and cubic close packing ( 3 ), respectively.Compounds 1 , 2 and 4 were synthesized as pure crystalline materials, their thermal behaviour was examined by TG/DTA measurements and temperature dependent PXRD. 1 , 2 and 4 show remarkable thermal stability with decomposition temperatures between 450 and 500 °C. Temperature dependent PXRD measurements of compounds 1 and 2 reveal a structural transition at 260 °C, framework 4 loses its crystallinity at 210 °C.