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Download fileDipoles Inside of Dipoles: Insertion Complexes of Polar versus Nonpolar Molecules in Ion Pairs
journal contribution
posted on 2017-06-05, 14:23 authored by Fedor Y. NaumkinHighly polar molecular
systems are in demand as a means of enabling
many important practical applications based on light–matter
interactions. In the present work, the insertion complexes of recently
synthesized polar molecules trapped between alkali halide counterions
are studied. For specific selected compositions, the M–molecule–X
systems are predicted to be stable to dissociation into molecule +
alkali halide. It is found that unlike their nonpolar molecule-based
counterparts, the polar molecule complexes can be even more stable
than their common dipole–dipole MX–molecule isomers.
This makes them thermodynamically stable, highly polar species, with
very large dipoles of about 20 D, and they could be used, for example,
to develop efficient light sensors. Furthermore, due to the neutralization
of the M–X charge transfer in the excited triplet state, such
complexes represent unique spin-controlled dipole-switch molecular
systems with the large dipole turned off and even inverted by the
spin state for the nonpolar and polar molecule complexes, respectively.
This potentially could allow various spintronic and optoelectronic
applications. In addition, the IR intensity spectra are predicted
to sensitively indicate the formation of both the M–molecule–X
and MX–molecule isomers, thus facilitating their reliable detection
and differentiation in experiments.