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Updated: Mar 24, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
Dynamics of Isolated 1,8-Naphthalimide and N-Methyl-1,8-naphthalimide: An Experimental and Computational Study
Thiemo Gerbich1, Hans-Christian Schmitt1, Ingo Fischer1
1Institute of Physical and Theoretical Chemistry, University of Würzburg , Am Hubland, D-97074 Würzburg, Germany.
Abstract:
In this work we investigate the excited-state structure and dynamics of the two molecules 1,8-naphthalimide (NI) and N-methyl-1,8-naphthalimide (Me-NI) in the gas phase by picosecond time- and frequency-resolved multiphoton ionization spectroscopy. The energies of several electronically excited singlet and triplet states and the S1 vibrational wavenumbers were calculated. Nonadiabatic dynamics simulations support the analysis of the radiationless deactivation processes. The origin of the S1 ← S0 (ππ*) transition was found at 30, 082 cm(-1) for NI and at 29, 920 cm(-1) for Me-NI. Furthermore, a couple of low-lying vibrational bands were resolved in the spectra of both molecules. In the time-resolved scans a biexponential decay was apparent for both Me-NI and NI. The fast time constant is in the range of 10-20 ps, whereas the second one is in the nanosecond range. In accordance with the dynamics simulations, intersystem crossing to the fourth triplet state S1 (ππ*) → T4 (nπ*) is the main deactivation process for Me-NI due to a large spin-orbit coupling between these states. Only for significant vibrational excitation internal conversion via a conical intersection becomes a relevant deactivation pathway.
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