Long-range
resonance energy transfer (RET) and the control of energy
transfer on the nanoscale have received considerable attention both
experimentally and theoretically during the past few decades. We have
investigated the RET between a donor/acceptor pair in the nanocavities
based on our previous theory developed in the framework of macroscopic
quantum electrodynamics (QED). On the basis of this theory, the enhancements
in the RET with respect to the rate in vacuum were evaluated for a
Fabry–Pérot cavity. When the displacement vector between
the two molecules is aligned with the cavity axis of the Fabry–Pérot
cavity, we find that cavity modes give enhancements of less than a
factor of 10 due to the interference between contributions from resonant
and non-resonant cavity modes. By comparison, when the displacement
vector between the two molecules is aligned in a plane perpendicular
to the cavity axis, we find that the cavity modes can induce enhancements
of more than a factor of 10, and the surface plasmon-polariton modes
can induce enhancements of up to a factor of 300. We develop a convenient
representation for understanding the effect of the displacement vector
between the molecules and of the molecular dipole directions in terms
of the H-dimer and J-dimer properties. To further enhance the RET,
we propose a square silver cavity that gives a rate enhancement of
a factor of 280 under cavity resonance conditions, which provides
important insight into developing devices capable of long-range RET.
Indeno[1,2‐b]fluorene‐based [2,2]cyclophanes with 4n/4n and 4n/[4n+2] π‐electron systems were prepared, and their structures were identified by X‐ray crystallography. With short π–π distances around 3.0 Å, [2.2](5,11)indeno[1,2‐b]fluorenophane and its precursor [2.2](5,11)indeno[1,2‐b]fluorene‐6,12‐dionophane exhibit remarkable transannular interactions, leading to their unusual electrochemical and photophysical properties. With the aid of femtosecond transient absorption spectroscopy, the transition from the monomeric excited state to the redshifted H‐type dimeric state was first observed, correlating to the calculated excitonic energy splitting and the steady‐state absorption spectra induced by charge‐transfer‐mediated superexchange interaction.
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