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Keys for the Existence of Stable Dimers of Bis-tetrathiafulvalene (bis-TTF)-Functionalized Molecular Clips Presenting [TTF]•+···[TTF]•+ Long, Multicenter Bonds at Room Temperature
journal contribution
posted on 2013-09-18, 00:00 authored by Maria Fumanal, Marçal Capdevila-Cortada, Joel S. Miller, Juan J. NovoaA systematic theoretical and computational
investigation is performed to determine the keys governing the existence,
in acetonitrile solutions, of dimers of bis-tetrathiafulvalene (bis-TTF)-functionalized
diphenylglycoluril molecular clips (clip2n+) that are stable at room temperature for n ≤ 4. Although the experimental structure of these dimers
in solution is unknown, electronic absorption studies suggest that
they have [TTF]l+···[TTF]m+ interactions that are preserved at room
temperature (note that when l = m = 1 these interactions become long, multicenter bonds). In good
agreement with the interpretation of the experimental spectroscopic
data, all clip2n+ dimers whose
charge is ≤4 present an optimum geometry that, in all cases,
has three short interfragment [TTF]l+···[TTF]m+ interactions. The computed ΔG(298 K) for these optimum structures matches the available
experimental data on the stability of these dimers. Such optimum geometry,
combined with the zwitterionic character of the electron distribution
in monomers and dimers (most of the net positive charge is equally
distributed among the TTF groups, while a 1– au charge is located
in the central fused five-membered rings) allows the formation of
a maximum of two long, multicenter [TTF]•+···[TTF]•+ bonds when all TTF groups host a 1+ au of charge,
as in clip24+. However, these long, multicenter
bonds alone do not account for the stability of clip2n+ dimers at room temperature. Instead, the
studies carried out here trace the origin of their stability to (1)
the zwitterionic character of their charge distribution, (2) the proper
geometrical shape of the interacting monomers, which allows the intercalation
of their arms, thus making possible the simultaneous formation of
two short contacts, both involving the positively charged TTF group
of one monomer and the negatively charged central ring of the other,
(3) the simultaneous presence of three short contacts among the TTF
groups in the optimum geometry of the clip2n+ dimers, which become two long, multicenter bonds
and one van der Waals interaction when the four TTF groups host a
1+ charge, and (4) the net stabilizing effect of the solvent.