2 research outputs found
Enantiodifferentiation in the Photoisomerization of (<i>Z</i>,<i>Z</i>)‑1,3-Cyclooctadiene in the Cavity of γ‑Cyclodextrin–Curcubit[6]uril-Wheeled [4]Rotaxanes with an Encapsulated Photosensitizer
A biphenyl photosensitizer axle was
implanted into the cavities
of native and capped γ-cyclodextrins through rotaxanation using
a cucubit[6]Âuril-templated azide–alkyne 1,3-dipolar cycloaddition,
resulting in the construction of highly defined chiral binding/sensitizing
sites. The orientation and interaction of the axle and capping moieties
at the ground and excited states were interrogated by NMR, UV–vis,
circular dichroism, and fluorescence spectroscopic studies. In situ
photoisomerization of (<i>Z</i>,<i>Z</i>)-1,3-cyclooctadiene
sensitized in the cavity of these [4]Ârotaxanes afforded (<i>Z</i>,<i>E</i>)-1,3-cyclooctadiene in up to 15.3% ee, which
represents the highest level of enantiodifferentiation obtained to
date for this supramolecular photochirogenesis
Supramolecular Photochirogenesis Driven by Higher-Order Complexation: Enantiodifferentiating Photocyclodimerization of 2‑Anthracenecarboxylate to Slipped Cyclodimers via a 2:2 Complex with β‑Cyclodextrin
Chiral
slipped 5,8:9′,10′-cyclodimers were preferentially
produced over classical 9,10:9′,10′-cyclodimers upon
supramolecular photocyclodimerization of 2-anthracenecarboxylate (AC)
mediated by β-cyclodextrin (β-CD). This photochirogenic
route to the slipped cyclodimers, exclusively head-to-tail (HT) and
highly enantioselective, has long been overlooked in foregoing studies
but is dominant in reality and is absolutely supramolecularly activated
by 2:2 complexation of AC with β-CD. The intricate structural
and photophysical aspects of this higher-order complexation-triggered
process have been comprehensively elucidated, while the absolute configurations
of the slipped cyclodimers have been unambiguously assigned by comparing
the experimental and theoretical circular dichroism spectra. In the
2:2 complex, two ACs packed in a dual β-CD capsule are not fully
overlapped with each other but are only partially stacked in a slipped <i>anti</i>- or <i>syn</i>-HT manner. Hence, they do
not spontaneously cyclodimerize upon photoexcitation but instead emit
long-lived excimer fluorescence at wavelengths slightly longer than
the monomer fluorescence, indicating that the slipped excimer is neither
extremely reactive nor completely relaxed in conformation and energy.
Because of the slipped conformation of the AC pair in the soft capsule,
the subsequent photocyclodimerization becomes manipulable by various
internal or external factors, such as temperature, pressure, added
salt, and host modification, enabling us to exclusively obtain the
slipped cyclodimers with high regio- and enantioselectivities. In
this supramolecularly driven photochirogenesis, the dual β-CD
capsule functions as a chiral organophotocatalyst to trigger and accelerate
the nonclassical photochirogenic route to slipped cyclodimers by preorganizing
the conformation of the encapsulated AC pair, formally mimicking a
catalytic antibody