Journal
CHEM
Volume 3, Issue 5, Pages 870-880Publisher
CELL PRESS
DOI: 10.1016/j.chempr.2017.09.005
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Funding
- Samsung Science and Technology Foundation [SSTF-BA1402-10]
- Japan Society for the Promotion of Science (JSPS) KAKENHI [25220802, 16K13952]
- JSPS
- National Research Foundation of Korea grants - Ministry of Education, Science, and Technology [NRF-2017R1A2A2A05001052, NRF-2014R1A4A1001690]
- Swedish Research Council [2015-04538]
- Swedish Research Council [2015-04538] Funding Source: Swedish Research Council
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The concept of excited-state aromaticity is receiving much attention in that completely reversed aromaticity in the excited state (so-called aromaticity reversal) provides crucial insight into photostability, photoreactivity, and its application to the photosynthetic mechanism and photoactive materials. Despite this significance, experimental elucidation of excited-state aromaticity is still unsolved, particularly for the excited singlet state. Here, as an unconventional approach, time-resolved IR (TRIR) spectroscopy on aromatic and anti-aromatic hexaphyrin congeners shed light on excited-singlet-state aromaticity. The contrasting spectral features between the Fourier transform IR and TRIR spectra reveal the aromaticity-driven structural changes, corroborating aromaticity reversal in the excited singlet states. Our paradigm for excited-state aromaticity, the correlation of IR spectral features with aromaticity reversal, provides another fundamental key to understanding the role of (anti) aromaticity in the stability, dynamics, and reactivity in the excited singlet state of p-conjugated molecular systems.
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