To determine structure-optical property relationships in asymmetric platinum acetylide complexes, we synthesized the compounds trans-Pt(PBu3)(2)( C CC6H5)(C C-C6H4-C CC6H5) (PE1-2), trans-Pt(PBu3)(2-)( C CC6H5)(C C-C6H4-C C-C6H4-C CC6H5) (PE1-3) and trans-Pt(PBu3)(2)(C C-C6H4-C CC6H5)( C C-C6H4-C C-C6H4-C CC6H5) (PE2-3) that have different ligands on either side of the platinum and compared their spectroscopic properties to the symmetrical compounds PE1, PE2 and PE3. We measured ground state absorption, fluorescence, phosphorescence and triplet state absorption spectra and performed density functional theory ( DFT) calculations of frontier orbitals, lowest lying singlet states, triplet state geometries and energies. The absorption and emission spectra give evidence the singlet exciton is delocalized across the central platinum atom. The phosphorescence from the asymmetric complexes comes from the largest ligand. Time-dependent (TD) DFT calculations show the S-1 state has mostly highest occupied molecular orbital (HOMO) -> lowest unoccupied molecular orbital (LUMO) character, with the LUMO delocalized over the chromophore. In the asymmetric chromophores, the LUMO resides on the larger ligand, suggesting the S-1 state has interligand charge transfer character. The triplet state geometries obtained from the DFT calculations show distortion on the lowest energy ligand, whereas the other ligand has the ground state geometry. The calculated trend in the triplet state energies agrees very well with the experimental trend. Calculations of triplet state spin density also show the triplet exciton is confined to one ligand. In the asymmetric complexes the spin density is confined to the largest ligand. The results show Kasha's rule applies to these complexes, where the triplet exciton moves to the lowest energy ligand.