The crystals of α,α’-dioxoketene cyclic dithioacetals were prepared and their crystal structures were determined by X-ray crystallography.The influence of bond lengths,bond angles,dihedral angles and the molecular conformation on different substituted cyclic dithionacetals aldehyde ketone was discussed.Compound A is Monoclinic form,P21/c Space group,Unit cell dimensions,a=0.78337（6）nm,b=O54937（4）nm,c=2.8243（2）nm,α=90°,β=90.7740（10）°,γ=90°,V=1.215（4）nm3,Z=4,Dc=1.445g/cm3,F（000）=552.Compound B is Orthorhombic form,P212121 Space group,Unit cell dimensions,a=0.5665（5）nm,b=0.7980（7）nm,c=2.924（3）nm,α=90°,β=90°,γ=90°,V=1.322（2）nm3,Z=4,Dc=1.399g/cm3,F（000）=584.
The electrochemical and spectral properties of four α,α′-dioxoketene cyclic dithioacetals were studied.All these compounds have only one quasi-reversible peak at around-1.4—-1.6 V on platinum microelectrode.The self-assembled monolayer film of these compounds was prepared on gold electrode and investigated by the electrochemical impedance spectroscopy(EIS) and X-ray photoelectron spectroscopy(XPS).The cyclic voltammogram peak potential and semicircle diameter were influenced by the number of methylenes and the substituting groups at one point of a ketone.
