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Syntheses, Structures, and Transannular π−π Interactions of Multibridged [3n]Cyclophanes1
journal contribution
posted on 1996-12-11, 00:00 authored by Youichi Sakamoto, Naomi Miyoshi, Mihoko Hirakida, Shirou Kusumoto, Haruo Kawase, Jerzy M. Rudzinski, Teruo ShinmyozuThe syntheses, conformational study, and transannular
π−π interaction of multibridged
[3n]cyclophanes
including the ultimate member of this series,
[36](1,2,3,4,5,6)cyclophane 1, are
described. The stepwise construction
of trimethylene bridges starting from
[33](1,3,5)cyclophane 6 led to the
synthesis of 1 by way of four- and five-bridged cyclophanes 7 and 8. The
variable-temperature (VT) 1H NMR study
(CD2Cl2) and molecular
mechanics
calculations (MM3) of five-bridged 8 revealed the most
stable conformer, the relative stability order of the
three
stable isomers, and energy barriers for the trimethylene bridge
inversion. A similar VT 1H NMR study
(toluene-d8)
of 1 suggests the presence of the trimethylene bridge
inversion process between two
C6h conformers. The
charge
transfer (CT) bands of the complexes of multibridged
[3n]cyclophanes with tetracyanoethylene
(TCNE) show significant
bathochromic shifts with the increase in the number of the bridges, and
this is mainly attributed to the effective
hyperconjugation between the benzyl hydrogens and the benzene rings.
The CT band of the TCNE−1 complex
(728 nm) is the longest wavelength among those of the TCNE complexes of
[m.n]cyclophanes and
multibridged
benzenophanes.
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Keywords
Cyclophanes 1charge transferbathochromic shiftstrimethylene bridge inversion processcyclophaneMM1 H NMR studytrimethylene bridgesCD 2 Cl 2benzene ringsTCNE complexesenergy barrierstrimethylene bridge inversionmultibridged benzenophanesmechanics calculationsVT 1 H NMR studybenzyl hydrogensC 6 h conformersCT bandstability order
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