Rb₃[PMo₁₂O₄₀], a compound containing Keggin anions

Abstract

Key indicators: single-crystal X-ray study; T = 293 K; mean (P-O) = 0.005 Å; R factor = 0.032; wR factor = 0.086; data-to-parameter ratio = 18.3.The cubic structure of trirubidium molybdophosphate, Rb 3 [PMo 12 O 40 ], contains -type Keggin [PMo 12 O 40 ] 3À anions and Rb + counter-ions located in orthogonally intersecting channels. The P and Rb atoms are located on special positions with site symmetries 43m and 42.m, respectively. The threedimensional arrangement is isostructural with that found in, for example, X 3 [PMo 12 O 40 ], with X = K, NH 4 and H 3 O, or X 3 [PW 12 O 40 ] and X 4 [SiW 12 O 40 ], with X = Ag and Tl. The compound was crystallized using a typical high-temperature solid-state reaction with GaPO 4 and X 3 Mo 3 O 10 (X = Rb or Li) as starting materials.

Top-down synthesis of polyoxometalate-like sub-nanometer molybdenum-oxo clusters as high-performance electrocatalysts

“…These distances are in agreement with those in POM-like Mo( vi ) oxo clusters, which typically feature shorter terminal Mo O bonds (∼1.7 Å) and longer, bridging Mo–O bonds (∼1.9 Å). 48 Note that these results are in agreement with the XANES analysis above. For 2 and 3 , we observe a weak Mo–P interaction which could indicate bonding between Mo and the P-doped carbon support and may also be associated with some amorphous, P-rich aggregates observed in the EDS mapping (see Fig.…”

Effect of Mo/P Ratios on Dimensions: Syntheses, Structures, and Properties of Three New Molybdophosphates

“…In addition, in our previous research, we also found an anomalous phase transition in the Mo­(VI)-containing phosphates, which would imply a potential application in negative expansion materials . However, remarkably, up to now only dozens of Mo­(VI)-containing phosphates have been reported. ,− Further exploration of Mo­(VI)-containing phosphates is still of scholarly and technological interest.…”

“…As shown in Figure , 12 MoO 6 octahedra connect with each other by sharing their equatorial O atoms to form a [Mo 12 O 40 ] spherical shell. A PO 4 tetrahedron as the core fills in the center of the [Mo 12 O 40 ] spherical shell to form the basic building unit (BBU), a 0D Keggin-type [Mo 12 PO 40 ] 3– cluster. ,, Further, these [Mo 12 PO 40 ] 3– clusters are separated by Cs + cations with a spacing of 4.484–4.493 Å to form the 0D structure of Cs 3 Mo 12 PO 40 (Figures b,c). All of the Cs + cations are 12-coordinated, and the range of Cs–O bond lengths is 3.154(2)–3.349(4) Å (Table S2).…”

“…Because of the Mo–O–P conenctions, the structural chemistry of the molybdophosphates is more flexible and variable. Many different dimensional connectivities of Mo–O–P have been observed in molybdophosphates: e.g., zero-dimensional (0D) Mo–O–P clusters, , one-dimensional (1D) Mo–O–P chains, , and three-dimensional (3D) Mo–O–P frameworks. ,− …”

“…37,38,50 Further, these [Mo 12 PO 40 ] 3− clusters are separated by Cs + cations with a spacing of 4.484−4.493 Å to form the 0D structure of Cs 3 Mo 12 PO 40 (Figures…”