Conformational interconversions in [2]catenanes containing a wide rigid bis(p-benzyl)methyl spacer.
The conformational interconversions of four [2]catenanes (1-4) containing a dibenzo-34-crown-10 ether (BPP34C10) interlocked with rings containing two 4,4'-dipyridiniums tethered by 1,3-bis(ethyloxy)phenyl and bis(p-benzyl)methyl spacers have been studied by VT 1H NMR spectroscopy. Symmetrically placed blocking groups on thickened tethers enabled either pathway for circumrotation of the BPP34C10 between isoenergetic sites to be blocked. On the basis of chemical shifts of the BPP34C10, its internal p-hydroquinone forms pi-pi-stacking interactions with only one 4,4'-dipyridinium ring at a time. The activation barrier for migration along either open tether was approximately 11.5 kcal/mol. This study demonstrates an ability to select the pathway for conformational interconversions in these [2]catenanes containing the rigid bis(p-benzyl)methyl tether and the lowering the barrier for interconversion through destabilization of the ground state structures.
Halterman
Ronald L
RL
Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, Oklahoma 73019, USA. rlhalterman@ou.edu
Pan
Xingang
X
Martyn
David E
DE
Moore
Jason L
JL
Long
Andrew T
AT
D043863:Catenanes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D021241:Spectrometry, Mass, Electrospray Ionization
D043863:Catenanes