Application of density functional theory for studies of excited states and phosphorescence of platinum(II) acetylides

The electronic states of different conformations of platinum acetylides Pt(PH3)(2)(C C-Ph)(2) and Pt(PH3)(2)(C C-PhC C-Ph)(2) (PE1 and PE2) were calculated with density functional theory (DFT) using effective core potential basis sets. Time dependent DFT calculations of UV absorption spectra showed strong dependence of the intense absorption band maxima on mutual orientation of the phenyl rings with respect to the P-Pt-P axis. Geometry optimization of the first excited triplet state (T-1) indicates broken symmetry structure with the excitation being localized in one ligand. This splits the two substitution ligands into a nondistorted aromatic ring with the C C-Ph bonds for one side and into a quinoid structure with a cumulenic C = C = C link on the other side. Quadratic response (QR) calculations of spin-orbit coupling and phosphorescence radiative lifetime (tau(R)) indicated a good agreement with experimental tau(R) values reported for solid PE1 and PE2 and PE2 capped with dendrimers in tetrahydrofuran solutions. The QR calculations reproduced an increase of tau(R) upon prolongation of pi chain of ligands and concommittant redshift of the phosphorescence. Moreover, it is shown how the phosphorescence borrows intensity from sigma ->pi(*) transitions localized at the C C-Pt-P fragments and that there is no intensity borrowing from delocalized pi ->pi(*) transitions.