| 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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