Rationalizing the Fluorescence Behavior of Core-Substituted Naphthalene Diimides
Sai Vamsi Krishna Isukapalli1, Priyanka Pushparajan1, Sivaranjana Reddy Vennapusa1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala PO, Vithura, Thiruvananthapuram, 695551, India.
Abstract:
We study the internal conversion (IC) and intersystem crossing (ISC) pathways of low-lying excited electronic states of three core-substituted naphthalene diimides (bNDI, yNDI, and gNDI) using wavepacket simulations within the linear vibronic coupling method. Our wavepacket simulations reproduce the experimental electronic absorption spectra very well. All molecules decay rapidly to S2 upon populating a higher dipole-allowed singlet excited-state. The S2 → S1 IC dynamics and singlet-triplet energy gap, spin-orbit coupling strength trends suggest a favorable S2 → T4 ISC in gNDI. The efficient ultrafast T4 formation and its decay to lower triplet states make gNDI nonfluorescent. Such triplet formation pathways are not operative in both bNDI and yNDI; hence, these molecules emit fluorescence from S1 after a slower S2 → S1 IC.
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