Synthesis, Crystal Structure And Properties Research Of Sandwich-type Compounds Constrcted From {SbW₉}

Five new supramolecular Sandwich Type Compounds Constructed From the[SbW₉O₃₃]9-Cluster have been synthesized by the routine synthetic reactions in anaqueous solution. The chemical formulas of five compounds have been determinedunder controlled conditions of pH and different organic ligands and characterized by IRspectroscopy, element analysis, thermal gravimetric analysis and single-crystal X-raydiffraction:[{Na₂（H₂O）₄（OH）₂}{Na（H₂O）₄}₂{（Zn（H₂O）₃）₂（W（H₂O）₂）₂(SbW₉O₃₃)₂}]·8H₂O （1）[{Na₂（H₂O）₄（OH）₂}{Na（H₂O）₄}₂{（Ni（H₂O）₃）₂（W（H₂O）₂）₂(SbW₉O₃₃)₂}]·16H₂O （2）[{Na₂（H₂O）₃（OH）₃}₂{（Mn（H₂O）₃）₂（W（H₂O）₂）₂(SbW₉O₃₃)₂}]·4H₃O·12H₂O （3）[{（Co（H₂O）₃）₂（WO2）₂(SbW₉O₃₃)₂}]·4[Co（H₂O）6]·2H₃O·16H₂O （4）[{Na（H₂O）₄}{Na3（H₂O）5}{Mn3（bpp）₂}(SbW₉O₃₃)₂}]·8H₃O（bpp=1,3-Di（4-pyridyl）propane）（5）These new compounds are structurally characterized by IR and single crystal X-raydiffractions. Single-crystal X-ray structural analysis reveals that the framework ofcompounds1-3are constructed from two trivacant [β-B-SbW₉O₃₃]9-linked by two[W（H₂O）₂]⁴⁺segments and two [M（H₂O）₃]²⁺（M=Zn, Ni, Mn） groups leading to the[M₂Sb₂W₂₀] units. The units are bonded by binuclear sodium cluster {Na₂（H₂O）₄（OH）₂}and {Na（H₂O）₄} linker （for compounds1and2） or by binuclear {Na₂（H₂O）₃（OH）₃}linker （for compounds3） to form infinite1-D chains. Compound4is isolated. Four[Co（H₂O₆）]²⁺anions are directly to the surface of the polyoxoanion. Compound5consists of sandwich-type [(α-B-SbW₉O₃₃)₂]^18-moieties linked throughcrystallographically independent Mn₃（bpp）₂and three Na+ions. Two Mn（bpp） iscoordinated by two Mn2+ions from another polyoxoanion which is linked by {Na（H₂O）₄}linker into a2-D structure. This is the first sandwich compound bridging the flexibleligand. By Electrochemical analysis system, the electrochemical and electrocatalyticbehaviors of compounds1-5have been investigated in detail. Compound5exhibitmagnetic properties and fluorescent properties.