Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V),[RPMo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(2-)(R=H,HO,CH_(3),HO_(2)CCH_(2...Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V),[RPMo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(2-)(R=H,HO,CH_(3),HO_(2)CCH_(2),HO_(2)CC_(2)H_(4),C_(6)H_(5),4-FC_(6)H_(4),4-F_(3)COC_(6)H_(4))and the monoanionic mixed-valent heptamolybdate[HOMo^(Ⅵ)Mo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(-).These nine novel polyanions feature a reduced,cyclic hexanuclear{Mo_(6)^(Ⅴ)O_(24)}core,decorated peripherally by three dimethylarsinate ligands and centrally by six different organophosphonate groups including fluorinated ones,as well as phosphate and phosphite.The polyanions were synthesized under simple one-pot aqueous solution conditions and characterized(i)in the solid state by single-crystal and powder XRD,TGA,elemental analysis,(ii)in solution by multinuclear(^(1)H,^(31)P,^(19)F,^(13)C)NMR,and(iii)in the gas phase by ESI mass spectrometry.展开更多
The title complex [Na (DB_18C_6) (H_2O)_2]_2Mo_6O_19·3DMF · 2CH_3OH (Ⅰ) , a new type of crown hexamolybdate supermolecule, has been synthesized. Its crystal structure has been determined by X-ray diffractio...The title complex [Na (DB_18C_6) (H_2O)_2]_2Mo_6O_19·3DMF · 2CH_3OH (Ⅰ) , a new type of crown hexamolybdate supermolecule, has been synthesized. Its crystal structure has been determined by X-ray diffraction analysis. The crystal C_49H_32 Mo_6N_2Na_2O_40 is tetragonal, space group P4/mbm, a= 17.108(2), c= 28. 285 (6) A ,V=8279(2) A￣ 3, Z=4 , M_r= 1960. 8 , D_x=1. 573 g/cm￣3 , P=9. 51cm￣(-1). F(000)=3936. The final agreement factors R=0. 058 and R_w= 0. 062 for 1777 independent reflections with F>4σ(F). In contrast to what we have reported about [Na(DB_18C_6)(CH_3OH)]_2Mo_6O_19(Ⅱ) where the whole complex was linked together, the cation [Na (DB_18C_6 ) (H_2O)_2]￣ + , that has crystallographic D_2h symmetry, combines with the anion with the symmetry O_h by electronic interaction.展开更多
文摘Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V),[RPMo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(2-)(R=H,HO,CH_(3),HO_(2)CCH_(2),HO_(2)CC_(2)H_(4),C_(6)H_(5),4-FC_(6)H_(4),4-F_(3)COC_(6)H_(4))and the monoanionic mixed-valent heptamolybdate[HOMo^(Ⅵ)Mo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(-).These nine novel polyanions feature a reduced,cyclic hexanuclear{Mo_(6)^(Ⅴ)O_(24)}core,decorated peripherally by three dimethylarsinate ligands and centrally by six different organophosphonate groups including fluorinated ones,as well as phosphate and phosphite.The polyanions were synthesized under simple one-pot aqueous solution conditions and characterized(i)in the solid state by single-crystal and powder XRD,TGA,elemental analysis,(ii)in solution by multinuclear(^(1)H,^(31)P,^(19)F,^(13)C)NMR,and(iii)in the gas phase by ESI mass spectrometry.
文摘The title complex [Na (DB_18C_6) (H_2O)_2]_2Mo_6O_19·3DMF · 2CH_3OH (Ⅰ) , a new type of crown hexamolybdate supermolecule, has been synthesized. Its crystal structure has been determined by X-ray diffraction analysis. The crystal C_49H_32 Mo_6N_2Na_2O_40 is tetragonal, space group P4/mbm, a= 17.108(2), c= 28. 285 (6) A ,V=8279(2) A￣ 3, Z=4 , M_r= 1960. 8 , D_x=1. 573 g/cm￣3 , P=9. 51cm￣(-1). F(000)=3936. The final agreement factors R=0. 058 and R_w= 0. 062 for 1777 independent reflections with F>4σ(F). In contrast to what we have reported about [Na(DB_18C_6)(CH_3OH)]_2Mo_6O_19(Ⅱ) where the whole complex was linked together, the cation [Na (DB_18C_6 ) (H_2O)_2]￣ + , that has crystallographic D_2h symmetry, combines with the anion with the symmetry O_h by electronic interaction.
