Communication
ChemComm
single crystals of the (R)-8-AgPF
6
complex were dissolved in
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CD
2
Cl
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/CD
3
OD, and the H NMR was measured (Fig. S35, ESI†).
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This revealed that the methyl group in the crystal structure
assigned as the doublets at the higher field (1.07 ppm) was one
of the thermodynamically stable structures (cis-(R,L)-isomer)
obtained from the molecular modelling calculations. The doublet
at the lower field (1.14 ppm), therefore, was assigned as the other
L-conformer (trans-(R,L)-isomer). Interestingly, when the solvent
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was changed to CD
and 0.90 ppm. In addition, two doublets appeared at 1.14 and
.07 ppm when the solvent was changed from CD CN to CD Cl /
3
CN, two doublets also appeared at ca. 0.98
3
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3 3
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ligand.
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In summary, we have prepared chiral tetra-armed cyclens
that show chiral enhancement and control of enantiomers
simultaneously upon metal complexation. Titration experi-
1
ments by CD, UV-vis, H NMR, and optical rotation exhibited
+
how the dynamic conformational change of a ligand by Ag
induced the chiral enhancement. These results were also
supported by X-ray crystal structures and DFT calculations.
This new chirality enhancement system induced by metal ions
provides a fresh perspective to asymmetric coordination chemistry.
This research was supported by Grant-in-Aid for Scientific
Research from the MEXT of Japan (Grant No. 23550164,
7737–7745.
9
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Conflicts of interest
(
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There are no conflicts to declare.
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