Ultrafast Processes in Isomeric Pyrene-N-methylacetamides: Formation of Hydrogen Bond Induced Static Excimers with Varied Coupling Strength.

Pyrene based molecules are inclined to form excimers through self-association upon photoexcitation. In this work, the pyrene core is functionalized with N-methylacetamide group at the position 1 or 2, to develop pyren-1-methylacetamide (PyMA1) and pyren-2-methylacetamide (PyMA2), respectively. Upon photoexcitation, PyMA1 and PyMA2, at 1.0mM, in toluene, have formed predominantly static excimers. The steady state spectroscopic studies have showed that the excitonic coupling of PyMA1 dimers are much stronger in solution than its isomeric counterpart, PyMA2. The transient absorption (TA) measurements over fs-ps regime (fs-TA) showed that the formation of static excimers with the strongly-coupled pre-associated dimers, in PyMA1, happens in approx. 560fs, whereas, the excimers for the weakly-coupled pre-associated dimers in PyMA2 have formed in much slower time scale (approx. 65ps). The introduction of methylacetamide group at the position 1 or 2 on pyrene ring, was believed to have allowed forming hydrogen bonded excimers with different degrees of excitonic coupling.