Coordination Chemistry of the Hexavacant Tungstophosphate [H₂P₂W₁₂O₄₈]¹²⁻ with Fe^III Ions: Towards Original Structures of Increasing Size and Complexity

Abstract

Sechs FeIII‐Zentren eingebaut: Das Wolframophosphatanion [H2P2W12O48]12− bildet mit FeCl3 {P2W12Fe6}‐Einheiten, die in [H4P2W12Fe9O56(OAc)7]6− und [H56P8W48Fe28O248]28− charakterisiert wurden. Letzteres ist ein supramolekulares Polyoxowolframat, in dem jede der vier {P2W12Fe6}‐Einheiten durch drei Fe‐O‐Fe‐Brücken verknüpft ist (siehe Struktur). Magnetismusstudien weisen auf eine starke antiferromagnetische Kopplung zwischen den FeIII‐Zentren hin.

Unprecedented Selenium and Lanthanide Simultaneously Bridging Selenotungstate Aggregates Stabilized by Four Tetra‐vacant Dawson‐like {Se2W14} Units

“…To put it another way, 1a can be understood as having two [Se 4 W 28 Tb 3 O 104 ] 15À fragments (Figure S7 ai nt he Supporting Information) that anchoro ne [W 8 Tb 2 O 24 (H 2 O) 10 ] 6 + group (Figure S7 bi nt he Supporting Information), forming aunique tetrameric ST aggregate [Se 8 W 64 Tb 8 O 208 (H 2 O) 10 ] 24À (Figure S7cin the Supporting Information), and then eight extraneous Se III atoms are incorporated into the ST aggregate and give rise to 1a (Figure S7di nt he Supporting Information). The 3D supramolecular packing alignments of 1 are illustrated inFigures S8 and S9(in the Supporting Information).As far as we know,s uch as tructural feature in which four multi-vacant Dawson fragments are connected by TM or Ln cations is very rare in POM chemistry.I ts hould be noted that the encapsulation mode of the multi-Se-Tb-W oxo clusterFigure 3a)s omewhat resembles that of the [H 47 WFe 27 O 56 ] 22 + {Fe 27 }c lusteri n[ H 55 P 8 W 49 Fe 27 O 248 ] 26À (7;F igure 3b)r eportedb y Gouzerh et al[20] It is not difficult to discover that several apparents tructural differences between them are observed: (a) both multi-vacant POM buildingb locks are significantly different, the multi-vacantP OM building block in 1 is the tetravacant Dawson-like[ Se 2 W 14 O 52 ] 12À fragment whereas the multivacant POM buildingb lock in 7 is the hexa-vacant Dawsontype [H 2 P 2 W 12 O 48 ] 12À fragment;( b) the intersection angles formed by two multi-vacantP OM building blocks in the half-Fe 13.5 O 28 ] 11 + cluster in 7 is at etradecanuclear Fe-W oxo cluster (…”

Hexadecacobalt(II)‐Containing Polyoxometalate‐Based Single‐Molecule Magnet

“…In particular lacunary heteropolytungstates of the Keggin and Wells–Dawson type are useful inorganic, diamagnetic ligands allowing for encapsulation of various multinuclear metal‐oxo assemblies. Examples of such kinds of structurally, catalytically, and magnetically interesting POMs are the manganese‐containing derivative {Mn 14 W 36 },2a the iron‐containing derivatives {Fe 9 W 12 },3a {Fe 13 W 36 },3b,c {Fe 16 W 48 },3d {Fe 28 W 48 },3e the nickel‐containing derivatives {Ni 9 W 27 },4a {Ni 8 /Ni 9 W 18 },4b {Ni 12 W 35 },4c and {Ni 20 W 34 },4d and the copper‐containing derivatives {Cu 14 W 36 }5a and {Cu 20 W 48 X} (X=Cl, Br, I) 5b,c. Some transition‐metal‐containing polyoxomolybdates are also known, such as {Fe 30 Mo 72 },6a {V 30 Mo 72 },6b as well as {Co 16 Mo 16 } (two types of structures containing 16 cobalt centers, in the form of four tetramers) 7…”

Poly(polyoxotungstate)s with 20 Nickel Centers: From Nanoclusters to One‐Dimensional Chains

“…One effective approach is to use high‐lacunary fragments as precursors to react with TM centers for making high‐nuclearity TM‐substituted POTs by conventional solution‐based methods. Resulting species include the Fe 28 ‐, Cu 20 ‐, Nb 16 ‐, and Ti 16 ‐substituted poly(POT)s [H 56 Fe 28 P 8 W 48 O 248 ] 28− ,2a [Cu 20 Cl(OH) 24 (H 2 O) 12 (P 8 W 48 O 184 )] 25− ,2b [Nb 4 O 6 (Nb 3 SiW 9 O 40 ) 4 ] 20− ,2c and [(P 2 W 15 Ti 3 O 62 ) 4 {Ti(OH) 3 } 4 Cl] 45− 2d. Recently [Ce 20 Ge 10 W 100 O 376 (OH) 4 (H 2 O) 30 ] 56− [2e] , substituted with 20 Ce centers, has also been made.…”