CFA-2 and CFA-3 (Coordination Framework Augsburg University-2 and -3); novel MOFs assembled from trinuclear Cu(i)/Ag(i) secondary building units and 3,3′,5,5′-tetraphenyl-bipyrazolate ligandsElectronic supplementary information (ESI) available: Atomic coordinates, bond lengths and angles, asymmetric units for 1, CFA-2 and CFA-3, XRPD patterns, SEM picture, IR, 1H NMR and 13C NMR spectra. CCDC 903114-903116. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3dt

The syntheses of H 2 -phbpz, [Cu 2 (phbpz)]·2DEF·MeOH ( CFA-2 ) and [Ag 2 (phbpz)] ( CFA-3 ) (H 2 -phbpz = 3,3′,5,5′-tetraphenyl-1 H ,1′ H -4,4′-bipyrazole) compounds and their crystal structures are described. The Cu( i ) containing metal-organic framework CFA-2 crystallizes in the tetragonal crystal system, within space group I 4 1 / a (no. 88) and the following unit cell parameters: a = 30.835(14), c = 29.306(7) Å, V = 27 865(19) Å 3 . CFA-2 features a flexible 3-D three-connected two-fold interpenetrated porous structure constructed of triangular Cu( i ) subunits. Upon exposure to different kinds of liquids (MeOH, EtOH, DMF, DEF) CFA-2 shows pronounced breathing effects. CFA-3 crystallizes in the monoclinic crystal system, within space group P 2 1 / c (no. 14) and the following unit cell parameters: a = 16.3399(3), b = 32.7506(4), c = 16.2624(3) Å, β = 107.382(2)°, V = 8305.3(2) Å 3 . In contrast to the former compound, CFA-3 features a layered 2-D three-connected structure constructed from triangular Ag( i ) subunits. Both compounds are characterized by elemental and thermogravimetric analyses, single crystal structure analysis and X-ray powder diffraction, FTIR- and fluorescence spectroscopy. Preliminary results on oxygen activation in CFA-2 are presented and potential improvements in terms of framework robustness and catalytic efficiency are discussed. Novel redox active MOFs containing trinuclear Cu( i )/Ag( i ) pyrazolate building units are described.