Abstract

The lowest triplet exciton state of crystals formed by ( C 6 H 5) 3− X− C ≡ C− C ≡ C− X−( C 6 H 5) 3 where X is Pb or Sn and an equimolecular amount of CH 2Cl 2 solvent molecules, is studied through the analysis of absorption and of phosphorescence emission and excitation spectra at low temperatures. In the lead compound, the origins of absorption and emission are identical, showing the dominance of free exciton emission and the absence of crystal lattice relaxation in the excited state; the splitting is accounted for by symmetry considerations in the different crystalline phases; the triplet exciton band is several cm -1 wide, although the nearest diacetylene-diacetylene distance is about 10 Å. There is evidence for triplet exciton motion, through the detection of trap (presumably X-trap) emission in the tin compound, and through the analysis of the excitation spectrum lineshape, showing the effect of exciton-exciton interaction in the lead compound.

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