Excited State Absorption Properties of Pt(II) Terpyridyl Complexes Bearing π-Conjugated Arylacetylides†

The synthesis, photophysics, and excited state absorption properties of three platinum(II) terpyridyl acetylide charge transfer (CT) complexes possessing a lone ancillary ligand systematically varied in phenylacetylide (PA) π-conjugation length, [Pt(tBu3tpy)([C≡C?C6H4]n?H)]ClO4 (n = 1, 2, 3), are described. Density functional theory (DFT) calculations performed on the ground states of complexes 1, 2, and 3 reveal that their HOMOs reside mainly on the ancillary π-conjugated PA moiety, ranging from 86 to 97%, with LUMOs predominantly centered on the terpyridyl acceptor ligand (91?92%). This electronic structure leads to the production of a triplet ligand-to-ligand CT (3LLCT) excited state upon visible light excitation with minor contributions from the corresponding triplet metal-to-ligand CT (3MLCT) excited state. Unusually strong red-to-near-IR transient absorptions are produced in the excited states of these molecules following selective long wavelength visible excitation of the low energy CT bands that do not emanate from the terpyridyl radical anion produced in the CT excited state or from an arylacetylide-based triplet intraligand (3IL) excited state. The extinction coefficients of these low energy absorption transients were determined using the energy transfer method with anthracene serving as the triplet acceptor. A detailed theoretical investigation using DFT and TDDFT methods reveals that these intense near-IR transient absorptions involve transitions resulting from transient oxidation of the PA subunit. In essence, the production of the 3LLCT excited state transiently oxidizes the PA moiety by one electron, producing the corresponding highly absorbing radical cation-like species, analogous to that experienced in related intramolecular photoinduced electron transfer reactions. The computational work successfully predicts the oscillator strength and peak wavelength of the measured excited state absorption transients across this series of molecules. In the present effort, there is a convergence of theory and experiment given that the excited state absorption properties of these Pt(II) chromophores are determined by localized transitions that resemble open shell radical cation species