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…
Cobalt-Containing Silicotungstate Sandwich Dimer [{Co3(B-β-SiW9O33(OH))(B-β-SiW8O29(OH)2)}2]22-
The 6-cobalt-substituted [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2]22- has been characterized by IR and UV-vis spectroscopy, elemental analysis, magnetic studies, electrochemistry, and gel filtration chromatography. A single-crystal X-ray analysis was carried out on K10Na12[{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2].49H2O (KNa-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a=19.9466(8) A, b=24.6607(10) A, c=34.0978(13) A, beta=102.175(1) degrees, and Z=2. Polyanion 1 represents a novel class of asymmetric sandwich-type polyanions. It contains three cobalt ions, which are encapsulated between an unprecedented (B-beta-SiW9O34) fragment and a (B-beta-Si…