Continuous Control of Optical Gaps in Quasi-One-Dimensional Bromide-Bridged Platinum Complexes by Utilizing Chemical Pressure

The optical gap in a series of bromo-bridged
platinum chain complexes, [Pt­(en)2Br]­(Cn–Y)2·H2O (en = ethylenediamine;
Cn–Y = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using
chemical pressure. From the single-crystal structure, [Pt­(en)2Br]­(C6–Y)2·H2O is in a mixed-valence state at 200 K. In addition, Pt–Pt
distances decreased with an increase in n or with
a decrease in the temperature. Continuous decreases in the optical
gaps upon cooling were observed for n = 5, 7. The
smallest gap of 1.20 eV was observed for n = 7 at
50 K. For n = 12, the complex was still in a mixed-valence
state at 5 K, although the Pt–Pt distance was quite short.
This is probably because of the energetic mismatch between 5dz2 orbitals of the Pt ions and
4pz orbitals of the Br ions.