Photophysical properties of self-assembled multinuclear platinum metallacycles with different conformational geometries

In this work, spectroscopic techniques and quantum chemistry calculations were used to investigate the photophysical properties of various multinuclear platinum complexes with different conformational geometries. This suite of complexes includes a Pt-pyridyl square, a Pt-carboxylate triangle, and a mixed Pt-pyridyl-carboxylate rectangle, as well as two mononuclear Pt model complexes. Studying the individual molecular precursors in the context of larger assemblies is important to provide a complete understanding of the factors governing the observed photophysical properties of a given system. The absorption and emission bands of the parent linear dipyridyl donor (ligand 1) are largely preserved in the [4 + 4] square and the multicomponent [4 + 2 + 2] rectangle (3 and 4, respectively), with significant red shifts. The [3 + 3] Pt-carboxylate triangle containing p-phthalic acid is nonemissive. Phosphorescence and nanosecond transient spectroscopy on 3 and 4 reveal that the introduction of platinum atoms enhances spin-orbital coupling, thereby increasing the rate of intersystem crossing. This phenomenon is consistent with the low fluorescence quantum yields and short fluorescence lifetimes of 3 and 4. Moreover, the electronic structures for the ground state and low-lying excited states of these compounds were studied using quantum chemistry calculations. The fluorescent states of the platinum complexes are local excited states of ligand-centered π-π* transition features, whereas the nonfluorescent states are intramolecular charge-transfer states. These low-lying intramolecular charge-transfer states are responsible for the nonemissive nature of small molecules 1 and 2 and triangle 5. As the interactions between these components determine the properties of their corresponding assemblies, we establish novel excited-state decay mechanisms which dictate the observed spectra.