Synthesis, Structure, and Properties of [Pt(II)(diimine)(dithiolate)] Dyes with 3,3‘-, 4,4‘-, and 5,5‘-Disubstituted Bipyridyl: Applications in Dye-Sensitized Solar Cells

A family of [Pt(II)(diimine)(dithiolate)] complexes of general formula [Pt{X,X‘(CO2R)2-2,2‘-bipyridyl}(maleonitriledithiolate)]
(where X = 3, 4, or 5 and R = H or Et) have been synthesized, spectroscopically and electrochemically characterized,
and attached to a TiO2 substrate to be tested as solar cell sensitizers. A single-crystal X-ray structure showing a
large torsion angle between the bipyridyl rings was determined for [Pt{3,3‘(CO2Et)2-2,2‘-bipyridyl}(maleonitriledithiolate)]·MeCN. The effect of changing the position of the bipyridyl substituents from 3,3‘ to 4,4‘ and 5,5‘ is discussed with
reference to structural and electronic changes seen within the different members of the family of molecules. The
first UV/vis/NIR spectroelectrochemical study of complexes of this general formula is discussed. All three complexes
(where R = H) were tested as solar cell sensitizers, with the 3,3‘-disubstituted bipyridyl complex giving an intermediate
dye loading value but superior photovoltaic performance to those of the other two. The performance of this sensitizer
is then compared with that of a well-known Ru polypyridyl sensitizer, the ditetrabutylammonium salt of [RuL2(NCS)2]
(L = 2,2‘-bipyridyl-4,4‘-dicarboxylato), commonly called N719.