Confinement
of Single Polysilane Chains in Coordination Nanospaces
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Abstract
Understanding
the intrinsic properties of single conducting polymer chains is of
interest, largely for their applications in molecular devices. In
this study, we report the accommodation of single polysilane chains
with hole-transporting ability in porous coordination polymers (PCPs),
[Al(OH)(L)]<sub><i>n</i></sub> (<b>1a</b>; L = 2,6-naphthalenedicarboxylate,
channel size = 8.5 × 8.5 Å<sup>2</sup>, <b>1b</b>;
L = 4,4′-biphenyldicarboxylate, channel size = 11.1 ×
11.1 Å<sup>2</sup>). Interestingly, the isolation of single polysilane
chains increased the values of carrier mobility in comparison with
that in the bulk state due to the elimination of the slow interchain
hole hopping. Moreover, even when the chains are isolated one another,
the main chain conformation of polysilane could be controlled by changing
the pore environment of PCPs, as evidenced by Raman spectroscopy,
solid-state NMR measurements, and molecular dynamics simulation. Hence,
we succeeded in varying the conducting property of single polysilane
chains. Additionally, polysilanes have a drawback, photodegradation
under ultraviolet light, which should be overcome for the application
of polysilanes. It is noteworthy that the accommodation of polysilane
in the nanopores did not exhibit photodegradation. These results highlight
that PCP–polysilane hybrids are promising candidates for further
use in the field of molecular electronics