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Sequence Matters: Modulating Electronic and Optical Properties of Conjugated Oligomers via Tailored Sequence
journal contribution
posted on 2013-02-26, 00:00 authored by Benjamin
N. Norris, Shaopeng Zhang, Casey M. Campbell, Jeffrey T. Auletta, Percy Calvo-Marzal, Geoffrey R. Hutchison, Tara Y. MeyerAlthough sequence must necessarily affect the photophysical
properties
of oligomers and copolymers prepared from donor and acceptor monomers,
little is known about this effect, as nearly all the donor/acceptor
materials have an alternating structure. A series of sequenced p-phenylene–vinylene (PV) oligomers was synthesized
and investigated both experimentally and computationally. Using Horner–Wadsworth–Emmons
(HWE) chemistry, a series of dimers, trimers, tetramers, pentamers,
and hexamers were prepared from two building block monomers, a relatively
electron-poor unsubstituted p-phenylene–vinylene
(A) and an electron-rich dialkoxy-substituted p-phenylene–vinylene
(B). UV–vis absorption/emission spectra and cyclic voltammetry
demonstrated that the optoelectronic properties of these oligomers
depended significantly on sequence. Calculations predicting the HOMO–LUMO
gap of the sequenced oligomers correlated well with the experimental
properties for the 2- to 4-mers, and the consensus model developed
was used to design hexameric sequences with targeted characteristics.
Despite the weak acceptor qualities of the “A” monomer
employed in the study, HOMO–LUMO gap differences of ∼0.25
eV were found for isomeric, sequenced oligomers. In no case did the
alternating structure give the largest or smallest gap. The use of
sequence as a strategy represents a new dimension in tailoring properties
of π-conjugated polymers.
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cyclic voltammetryoptoelectronic propertiesbuilding block monomersseriesConjugated OligomersPVSequence MattersUVHOMOphotophysical propertiesTailored SequenceAlthough sequenceHWEgapconsensus modelModulating Electronicacceptor qualitiesoligomerdonorOptical Propertiesacceptor monomersdesign hexameric sequences
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