Controlling the Orientation of Pendants in Two-Dimensional
Comb-Like Polymers by Varying Stiffness of Polymeric Backbones
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Abstract
The electronic communications between
chromophores are closely
related to distances and orientation of these π-conjugated systems.
Reported herein is a collection of well-defined two-dimensional comb-like
polymers containing porphyrin pendants obtained by ring-opening metathesis
polymerizations of norbornene and cyclobutene derivatives using ruthenium
or molybdenum catalysts. The spacing separating the adjacent pendants
are defined by ring sizes of cycloalkenes and the orientations are
determined by the stiffness of the polymeric backbone, which is, in
turn, discerned by the percentage of <i>Z</i>-double bonds.
Both peak widths of the porphyrin radical cation of the EPR spectra
and the absorption profiles in the Soret band region reflect the degree
of the spin delocalization and exciton coupling between porphyrin
pendants in these polymers and, hence, the stiffness of the polymeric
backbone. Our approach offers a useful protocol to align an array
of chromophores appended onto a rigid polymeric backbone so that the
optoelectronic properties can be tuned