Two rare mixed-cluster-organic frameworks (CH3NH3)3[Cu4-(μ3-O)2(Lb)4][MnMo6O18(La)2]·4NMF·5H2O (1) and [(CH3)2NH2]3[Co5-(μ3-O)2(Lb)6]-[MnMo6O18(La)2]·5DMF (2) (La = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol; Lb = 4-(2-(4-pyridyl)ethenyl) benzoic acid; NMF = N-methylformamide; DMF = N,N-dimethylformamide) have been obtained, exhibiting the first two porous materials simultaneously integrating polyoxometalates and transition-metal–oxygen clusters as secondary building units (SBUs).
