Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 99, Issue 8, Pages 5007-5011Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.062656699
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The inclusion behavior of methylviologen (N,N'-dimethyl-4,4'-bipyridinium, MV) dication in cucurbit[7]uril (CB[7]) has been studied by using various spectroscopic and electrochemical methods. The inclusion complex of MV dication in CB[7] is stable thermodynamically and kinetically. The electrochemical study reveals that unlike P-cyclodextrin, CB[7] prefers the charged species, MV dication (MV2+), and cation radical (MV+.) to the fully reduced neutral (MV0) species as guests. Dimerization of MV+. is suppressed effectively by forming a stable complex with CB[7] in aqueous solution as confirmed by spectroelectrochemical experiments. Furthermore, the first redox process (MV2+/MV+.) of the MV2+-CB[7] complex occurs predominantly via the direct electron transfer pathway, whereas the second redox process (MV+./MV0) occurs via both the direct and indirect pathway because of the low affinity of the fully reduced species MV0 to CB[7].
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