| In this paper, on the basis of molecular design and assembly, we report eleven new inorganic-organic hybrid heteropolyoxomolybdates were synthesized by a simple one-pot reaction of?NH4?6Mo7O24·4H2O/Na2MoO4·2H2O, H3PO3/As2O3/Sb2O3, and corresponding v-type aromaticcarboxylicacids in aqueous medium. These hybrids exhibit different structures such as dimer, trimer, tetramer and hexamer. These complexes were charactered by single-crystal X-ray diffraction, X-ray diffraction?XRD?, spectroscopic properties?IR, UV?, thermogravimetric analyses?TG?. In addition, the photochromism and thermochromism of these compounds were studied systematically.This dissertation contains:1. Three heteropolyoxomolybdates constructed by pyridine-2,6-dicarboxylic acid Cs3.5?NH4?11H3.5[(HPMo6O21)2(HPMo6O23){C5H3N?COO?2}4]·19H2O?1?,Cs5Na8H13[(AsMo6O21)4{C5H3N?COO?2}7]·32H2O?2?,Cs7.5?NH4?12H1.5[(SbMo6O21)2(SbMo6O23){C5H3N?COO?2}4]·27H2O?3? have been obtained?Polyoxoanions of 1 and 3 have the same structure that three {XMo6}?X = P, Sb? clusters linked by four carboxylic acid groups, giving the anion a cage structure. Polyoxoanions of 1 include four {AsMo6} units joined together by seven V-type aromaticcarboxylicacid ligands to form the asymmetric unit of polyanion with ship type.2. Five heteropolyoxomolybdates constructed by benzene-1,3-dicarboxylic acid :?NH4?10[(HPMo6O21)2?HPO3?{C6H4?COO?2}2]·14H2O?4?,[?CH3?4N]2?NH4?8[(HPMo6O21)2?HPO3?{C6H4?COO?2}2]·15.5H2O?5?,?NH4?17H4[(AsMo6O21)2(AsMo6O23){C6H4?COO?2}4]·28H2O?6?,?NH4?15Cs6[(AsMo6O21)2(AsMo6O23){C6H4?COO?2}4]·26H2O?7?,Cs9?NH4?12[(SbMo6O21)2(SbMo6O23){C6H4?COO?2}4]·33H2O?8??Compound 4 and 5 have the same structure that two [HPMo6O21]2– units were connected by one [HPO3]2- unit and two benzene-1,3-dicarboxylic acid linkers. Polyoxoanions of 6-8 have the similar structure with compound 1.3. Two heteropolyoxomolybdates constructed by 5-hydroxy-1,3-benzenedicarboxylic acid :?NH4?9H[(HPMo6O21)2?HPO3?{C6H3OH?COO?2}2]·14H2O?9?,?NH4?5Cs8H6[(AsMo6O21)3{C6H3OH?COO?2}5]·40H2O?10??Polyoxoanions of compound 10 have the similar structure with compound 4. Polyoxoanions of 10 contain three {AsMo6} clusters linked by five carboxylic acid ligands, giving the anion a cage structure.4. A phosphomolybdate constructed by pyridine-3,5-dicarboxylic acid :[N?CH3?4]6?NH4?19H3[(HPMo6O21)6?HPO3?2{C5NH3?COO?2}6]·48H2O?11??Polyoxoanions of 11 contain six {PMo6} clusters linked by six carboxylic acid ligands and two [HPO3]2- units, giving the anion a structure of telephone. |
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