The direct observations of delayed fluorescence and phosphorescence from the cyanine dye Cy5 are reported. The delayed fluorescence is generated from the S(1) state of trans-Cy5 through a reserve intersystem crossing from the cis-triplet state T(1) to the trans-singlet state S(1) via thermal activation. The lowest cis-triplet state is evidenced to be involved in the formation of the isomer. The back-isomerization from cis-triplet state to trans-singlet state crossing, a remarkably back-isomerization pathway that has not been reported before, plays a significant role in this unusual delayed fluorescence.
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