AbstractAttempts to synthesize Pr4Mo7O27 using Pr, Pr6O11 and MoO3 in a molar ratio of 8:6:77 led to a main product of scheelite-type Pr0.667[MoO4] and few single crystals of the triclinic A-type Pr6Mo10O39. The latter crystallizes in space group P1̅ (a=945.25(1), b=1058.49(2), c=1815.16(3) pm; α=104.149(1), β=95.220(1), γ=102.617(1)°, Z=2). Its crystal structure comprises six crystallographically independent Pr3+ cations, eight tetrahedral [MoO4]2− units, and one [Mo2O7]2− entity. The cations display coordination numbers of seven (1×) and eight (5×), while the [MoO4]2− tetrahedra are surrounded by five Pr3+ cations each. The [Mo2O7]2− anions exhibit a coordination environment of seven Pr3+ cations. The attempt to synthesize PrF[MoO4] using PrOF (from in situ thermal decomposition of PrF[CO3]) as reagent did not lead to the desired product but to monoclinic B-type Pr6Mo10O39. This slightly less dense modification compared to its triclinic analogue crystallizes in space group C2/c (a=1247.93(3), b=1989.68(6), c=1392.52 (4) pm, β=100.505(2)°, Z=4) with three crystallographically independent Pr3+ cations, four [MoO4]2− tetrahedra, and again one [Mo2O7]2− unit in the crystal structure. Thus, both Pr6Mo10O39 modifications are better described with the structured formula Pr6[MoO4]8[Mo2O7]. The coordination numbers around the Pr3+ cations are seven (1×) and eight (2×) while all four [MoO4]2− anions are again surrounded by five Pr3+ cations each. Six of the latter represent the coordination environment around the [Mo2O7]2− entities. Besides the thorough comparison of the crystal structures single crystal Raman spectra were recorded for both Pr6Mo10O39 phases.
In situ Synchrotron IR Microspectroscopy of CO2Adsorption on Single Crystals of the Functionalized MOF Sc2(BDC-NH2)3