0000000000184377
AUTHOR
Santiago Reinoso
ChemInform Abstract: Giant Crown-Shaped Polytungstate Formed by Self-Assembly of CeIII-Stabilized Dilacunary Keggin Fragments.
Single crystals of Na40K6[Ni(H2O)6]3 [K@K7Ce24Ge12W120O456 (OH)12(H2O)64]· 178H2O are synthesized by addition of KCl to a NaOAc/AcOH buffer solution containing Ce(NO3)3, GeO2, Na2WO4, and NiCl2 followed by slow evaporation at room temperature (24% yield).
Heterometallic 3d–4f polyoxometalates: still an incipient field
Heterometallic 3d-4f polyoxometalates still remain as an almost unexplored class of polyoxoanions despite showing great potential in fields such as molecular magnetism. This Frontier reviews some of their synthetic, structural and magnetic features and gives a personal view on future research in this area.
Giant Crown-Shaped Polytungstate Formed by Self-Assembly of CeIII-Stabilized Dilacunary Keggin Fragments
Single crystals of Na40K6[Ni(H2O)6]3 [K@K7Ce24Ge12W120O456 (OH)12(H2O)64]· 178H2O are synthesized by addition of KCl to a NaOAc/AcOH buffer solution containing Ce(NO3)3, GeO2, Na2WO4, and NiCl2 followed by slow evaporation at room temperature (24% yield).
pH‐Controlled Assemblies of Dimethyltin‐Functionalized 9‐Tungstophosphates with Guanidinium as Structure‐Directing Cation
Aqueous reaction of (CH 3 ) 2 SnCl 2 with Na 9 [A-α-PW 9 O 34 ] in a 3:1 ratio with [C(NH 2 ) 3 ] + as structure-directing agent resulted in three distinct assemblies of dimethyltin-functionalized tungstophosphates depending on the pH: [{(CH 3 ) 2 -Sn(H 2 O)}{(CH 3 ) 2 Sn}(A-α-PW 9 O 34 )] 5- ( 1 ) at pH = 4.5; [{(CH 3 ) 2 -Sn(H 2 O) 2 }{(CH 3 ) 2 Sn(H 2 O)} 2 (A-α-PW 9 O 34 )] 3- (2) at pH = 3.0; and [{(CH 3 ) 2 Sn(H 2 O)} 3 (A-α-PW 9 O 34 )] 3- (3) at pH = 2.0. All three compounds have been characterized in the solid-state by elemental and thermal analyses, infrared spectroscopy and single-crystal X-ray diffraction. The [A-α-PW 9 O 34 ] 9- trilacunary fragments have three {(CH 3 ) 2 Sn} 2…
Heterometallic 3d−4f Polyoxometalate Derived from the Weakley-Type Dimeric Structure
Polyanion [{Ce(H(2)O)(2)}(2)Mn(2)(B-alpha-GeW(9)O(34))(2)](8-) (1) constitutes the first example of a heterometallic 3d-4f cluster related to the Weakley-type dimeric structure, and it contains an unprecedented Ce(III)(2)Mn(III)(2)O(20) rhomblike moiety displaying dominant Ce(III)-Mn(III) ferromagnetic interactions.
Selective Crystallization of Dimeric vs. Monomeric Dimethyltin‐Containing Tungstoarsenates(III) and ‐antimonates(III) with the Guanidinium Cation
The use of guanidinium cations [C(NH 2 ) 3 ] + as crystallizing agents allowed us to selectively isolate the dimeric [{(CH 3 ) 2 -Sn(H20)} 4 {(CH 3 ) 2 Sn}(B-β-XW 9 O 33 ) 2 ] 8- (1, X = As III ; 2, X = Sb III ) polyanions from the reaction of (CH 3 ) 2 SnCl 2 with Na 9 [B-a-XW 9 O 33 ) (3:1 ratio) in water at pH 3. This reaction is known to give the monomeric [{(CH 3 ) 2 Sn(H 2 O) 2 } 3 (B-β-XW 9 O 33 )] 3- polyanions as the major species. Polyanions 1 and 2 are composed of one octahedral trans-(CH 3 ) 2 SnO 4 moiety that bridges two trilacunary [B-β-XW 9 O 33 ] 9- Keggin subunits further decorated by two structurally nonequivalent {(CH 3 ) 2 Sn} 2+ functionalities each: one distorted octa…