Controlling the Degree
of Polymerization, Bond Lengths,
and Bond Angles of Plasmonic Polymers
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Abstract
Plasmonic polymers present an interesting concept that
builds on
the analogy between molecular polymers and linear chains of strongly
interacting metal nanoparticles. Ensemble-averaged optical properties
of plasmonic polymers are strongly influenced by their structure.
In the present work, we formed plasmonic polymers by using solution-based
assembly of gold nanorods (NRs) end-tethered with photoactive macromolecular
tethers. By using postassembly ligand photo-cross-linking, we established
a method to arrest NR polymer growth after a particular self-assembly
time, and in this manner, using kinetics of step-growth polymerization,
we achieved control over the average degree of polymerization of plasmonic
polymers. Photo-cross-linking of ligands also enabled control over
the internanorod distance and resulted in the increased rigidity of
NR chains. These results, along with a higher structural integrity
of NR chains, can be utilized in plasmonic nanostructure engineering
and facilitate advanced applications of plasmonic polymers in sensing
and optoelectronics