Conspectus
One of the most desirable and advantageous attributes of organic
materials chemistry is the ability to tune the molecular structure
to achieve targeted physical properties. This can be performed to
achieve specific values for the ionization potential or electron affinity
of the material, the absorption and emission characteristics, charge
transport properties, phase behavior, solubility, processability,
and many other properties, which in turn can help push the limits
of performance in organic semiconductor devices. A striking example
is the ability to make subtle structural changes to a conjugated macromolecule
to vary the absorption and emission properties of a generic chemical
structure.
In this Account, we demonstrate that target properties
for specific
photonic applications can be achieved from different types of semiconductor
structures, namely, monodisperse star-shaped molecules, complex linear
macromolecules, and conjugated polymers. The most appropriate material
for any single application inevitably demands consideration of a trade-off
of various properties; in this Account, we focus on applications such
as organic lasers, electrogenerated chemiluminescence, hybrid light
emitting diodes, and visible light communications. In terms of synthesis,
atom and step economies are also important. The star-shaped structures
consist of a core unit with 3 or 4 functional connection points, to
which can be attached conjugated oligomers of varying length and composition.
This strategy follows a convergent synthetic pathway and allows the
isolation of target macromolecules in good yield, high purity, and
absolute reproducibility. It is a versatile approach, providing a
wide choice of constituent molecular units and therefore varying properties,
while the products share many of the desirable attributes of polymers.
Constructing linear conjugated macromolecules with multifunctionality
can lead to complex synthetic routes and lower atom and step economies,
inferior processability, and lower thermal or chemical stability,
but these materials can be designed to provide a range of different
targeted physical properties. Conventional conjugated polymers, as
the third type of structure, often feature so-called “champion”
properties. The synthetic challenge is mainly concerned with monomer
synthesis, but the final polymerization sequence can be hard to control,
leading to variable molecular weights and polydispersities and some
degree of inconsistency in the properties of the same material between
different synthetic batches. If a champion characteristic persists
between samples, then the variation of other properties between batches
can be tolerable, depending on the target application. In the case
of polymers, we have chosen to study PPV-type polymers with bulky
side groups that provide protection of their conjugated backbone from
π–π stacking interactions. These polymers exhibit
high photoluminescence quantum yields (PLQYs) in films and short radiative
lifetimes and are an important benchmark to monodisperse star-s...