Communications
DOI: 10.1002/anie.201003291
p-Conjugated Polymers
Tuning the Singlet–Triplet Gap in Metal-Free Phosphorescent
p-Conjugated Polymers**
Debangshu Chaudhuri, Henning Wettach, Kipp J. van Schooten, Su Liu, Eva Sigmund,
Sigurd Hꢀger,* and John M. Lupton*
Much of the fascination in conjugated polymers stems from
the realization of potential device applications,[1] yet the true
power of these materials lies in the possibility to synthesize a
compound with a particular property from first principles. A
defining feature of these carbon-based semiconductors is that
spin–orbit coupling is weak, thus making spin states well-
defined.[2–3] Electrical injection of charges into an organic
light-emitting diode (OLED) leads to triplet and singlet
excitations with symmetric or antisymmetric spin wavefunc-
tions. As triplet excitations are typically not dipole-coupled to
the molecular ground state, the majority of carrier pairs that
recombine in an OLED decay nonradiatively. Incorporation
of heavy-atom centers that are mostly in the form of an
organometallic luminophore and promote spin–orbit cou-
pling, is employed to promote radiative triplet recombina-
tion.[4]
The direct spectroscopic identification of triplet excita-
tions in conjugated polymers became possible by detecting
the weak phosphorescence.[5] In this approach, the relative
energies of the singlet and triplet excitations are determined
by comparing prompt fluorescence to delayed phosphores-
cence, thus directly revealing the exchange energy. Although
small-molecule organometallic complexes display a variety of
exchange interaction strengths,[4e,f] it has been proposed that
the singlet and triplet excited state are universally split by
some 0.7 eV in conjugated polymers.[3c] Here, we present a
new series of triphenylene-based metal-free conjugated
copolymers with tunable exchange splitting, which is revealed
by their distinct fluorescence and phosphorescence signa-
tures. In addition, we show how both singlet and triplet
excited states can couple to emissive defects, hence revealing
the fundamental mechanism for color purity degradation that
is a common problem for poly(para-phenylene)s such as
polyfluorenes.[6]
Most conjugated hydrocarbons show either weak phos-
phorescence or no phosphorescence at all.[3] Triphenylenes,
and some other polycyclic aromatic hydrocarbons, are an
exception: at low temperatures, they exhibit a pronounced
afterglow, which is often attributed to the phosphorescence
from the triplet state.[7] Although triphenylene-based com-
pounds have recently been investigated as blue singlet
emitters in OLEDs,[8] the relevance of the triplet states to
OLEDs has not yet been considered.
In the polymers presented herein, the triphenylene 1 is an
integral part of the polymer backbone (Figure 1). Incorpo-
ration of 1 into the backbone leads to a fully conjugated
p system in which the triplet state is localized on the
triphenylene unit, yet the singlet state is delocalized over
multiple repeat units (Figure 1a). We synthesized the poly-
mer 2 from 1,[9] along with four different copolymers 3–6 by
using transition-metal-catalyzed polycondensation. The
prompt and delayed luminescence of the compounds dis-
persed at a 1% weight ratio in polystyrene at 25 K is shown in
Figure 1b–g. The prompt luminescence (detected in a 2 ns
time window that coincides with the laser pulse) is caused by
fluorescence from the singlet state, whereas the delayed
emission (detected several hundred microseconds after exci-
tation) can be assigned to phosphorescence from the triplet
state.[7] A similar triplet spectrum is observed for all materials
(the average peak position is marked by a dashed line),
whereas the singlet peak strongly depends on the intricacies
of the polymer backbone.[9] The energetic separation between
fluorescence and phosphorescence provides an accurate
measure of the magnitude of the exchange interaction
(2J).[3] From 1 to 6, the singlet emission shifts to the red,
while the triplet emission remains unchanged:[9] copolymer 6
has almost degenerate singlet and triplet levels. This degen-
eracy is unprecedented in conjugated polymers and is
particularly surprising given the fact that the triplet level of
regular poly(thienylene vinylene) lies at 1170 nm.[3i] Appa-
rently, singlet and triplet excitations can form on different
parts of the conjugated system,[10] thus allowing the splitting to
be tuned. The series in Figure 1 suggests that it may be
possible to design materials in which the regular level
ordering is reversed, so that the singlet state lies energetically
beneath the triplet state.
[*] Dr. D. Chaudhuri, K. J. van Schooten, S. Liu, Prof. Dr. J. M. Lupton
Department of Physics and Astronomy
University of Utah
Salt Lake City, UT 84112 (USA)
Fax: (+1)801-581-4801
E-mail: lupton@physics.utah.edu
Dr. H. Wettach, E. Sigmund, Prof. Dr. S. Hꢀger
Kekulꢁ-Institut fꢂr Organische Chemie und Biochemie
der Universitꢃt Bonn
Gerhard-Domagk-Str. 1, 53121 Bonn (Germany)
Fax: (+49)228-73-5662
E-mail: hoeger@uni-bonn.de
[**] We thank the Volkswagen Foundation for collaborative research
funding. J.M.L. is a David and Lucile Packard Foundation Fellow and
is indebted to the NSF (grant CHE-ASC 0748473) and the DoE
(grant DESC0000909) for financial support.
The singlet and triplet states of the polymer are not the
only spectral signatures seen in 1–6. Poly(para-phenylene)s
are prone to the formation of oxidative defects that result in
broad emission spectra, as has been studied in particular
Supporting information for this article is available on the WWW
7714
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2010, 49, 7714 –7717