The dynamics of interchain and intrachain excitation energy transfer taking place in a polyindenofluorene endcapped with perylene derivatives is explored by means of ultrafast spectroscopy combined with correlated quantum-chemical calculations. The experimental data indicate faster exciton migration in films with respect to solution as a result of the emergence of efficient channels involving hopping between chains in close contact. These findings are supported by theoretical simulations based on an improved Forster model. Within this model, the rates are expressed according to the Fermi golden rule on the basis of (i) electronic couplings that take account of the detailed shape of the excited-state wave functions (through the use of a multicentric monopole expansion) and (ii) spectral overlap factors computed from the simulated acceptor absorption and donor emission spectra with explicit coupling to vibrations (considered within a displaced harmonic oscillator model); inhomogeneity is taken into account by assuming a distribution of chromophores with different conjugation lengths. The calculations predict faster intermolecular energy transfer as a result of larger electronic matrix elements and suggest a two-step mechanism for intrachain energy transfer with exciton hopping along the polymer backbone as the limiting step. Injecting the calculated hopping rates into a set of master equations allows the modeling of the dynamics of exciton transport along the polyindenofluorene chains and yields ensemble-averaged energy-transfer rates in good agreement with experiment.

The energy-transfer processes taking place in conjugated polymers are investigated by means of ultrafast spectroscopy and correlated quantum-chemical calculations applied to polyindenofluorenes end-capped with a perylene derivative. Comparison between the time-integrated luminescence and transient absorption spectra measured in solution and in films allows disentangling of the contributions arising from intrachain and from interchain energymigration phenomena. Intrachain processes dominate in solution where photoexcitation of the polyindenofluorene units induces a rather slow energy transfer to the perylene end moieties. In films, close contacts between chains favors interchain transport of the excited singlet species (from the conjugated bridge of one chain to the perylene unit of a neighboring one); this process is characterized by a 1-order-of-magnitude increase in transfer rate with respect to solution. This description is supported fully by the results of quantum-chemical calculations that go beyond the usual pointdipole model approximation and account for geometric relaxation phenomena in the excited state before energy migration. The calculations indicate a two-step mechanism for intrachain energy transfer with hopping along the conjugated chains as the ratelimiting step; the higher efficiency of the interchain transfer process is mainly due to larger electronic coupling matrix elements between closely lying chains. E nergy transfer is a key process in the working mechanism of a number of opto-electronic devices based on conjugated materials. This is the case for instance in electroluminescent displays where one can take advantage of energy transfer to tune the color of the emitted light when the active layer includes several materials with different optical gaps (1-5). In addition to providing an efficient technique for internal color conversion, polymer-polymer and polymer-dye blends have been shown also to lead to a significant improvement in photoluminescence (PL) and electroluminescence (EL) quantum efficiencies (6-8).Since most conjugated polymers are characterized by the presence of a distribution of segments with distinct conjugation lengths, optical absorption in the inhomogeneously broadened density of states usually leads to unidirectional energy migration to lower energy sites (9). Thus, controlling the flow of excitations across the polymer material is of importance to limit luminescence quenching due to energy transfer to defects.In the case of solar cells, charge generation usually requires the migration of the electronic excitations induced by light absorption toward dissociation zones (such as interfaces in blends made of different materials) (10, 11). Research in this field aims at mimicking the powerful antenna machines that nature has designed through evolution to harvest solar light and funnel the energy to the photosynthetic reaction centers (12).A most striking demonstration of ultrafast energy transfer in conjugated polymers is the recent discovery of highly sensitive biological an...

We report combined experimental and theoretical studies of excitation relaxation in poly[2-methoxy,5-(2'-ethyl-hexoxy)-1,4-phenylenevinylene] (MEH-PPV), oligophenylenevinylene (OPV) molecules of varying length, and model PPV chains. We build on the paradigm that the basic characteristics of conjugated polymers are decided by conformational subunits defined by conjugation breaks caused by torsional disorder along the chain. The calculations reported here indicate that for conjugated polymers like those in the PPV family, these conformational subunits electronically couple to neighboring subunits, forming subtly delocalized collective states of nanoscale excitons that determine the polymer optical properties. We find that relaxation among these exciton states can lead to a decay of anisotropy on ultrafast time scales. Unlike in Forster energy transfer, the exciton does not necessarily translate over a large distance. Nonetheless, the disorder in the polymer chain means that even small changes in the exciton size or location has a significant effect on the relaxation pathway and therefore the anisotropy decay.

Poly(fluorene)-type materials are widely used in polymer-based light emitting devices. In their pristine state, they emit in the deep blue spectral region. During operation there appears, however, an additional emission peak at around 2.3 eV. This observation has usually been attributed to aggregate or excimer formation. Recently, it has been shown that photo- and/or electro-oxidation of poly(fluorene) chains resulting in ketonic defects (i.e., formation of fluorenone groups) can also be held responsible for emission in that spectral region. In this contribution, we apply quantum-chemical techniques to gain a detailed understanding of the optical properties of poly(fluorene)s containing ketonic defects. In particular, we compare model systems for poly(fluorene) with their ketone-containing counterparts, focusing on the influence of excited-state localization effects. The results of the theoretical calculations are confirmed by experimental investigations on statistical copolymers of fluorene and 9-fluorenone.

Articles you may be interested inExcited state calculations on fluorene-based polymer blends: Effect of stacking orientation and solvation Theoretical and experimental studies of the opto-electronic properties of positively charged oligo(phenylene vinylene)s: Effects of chain length and alkoxy substitutionWe report a detailed quantum-chemical characterization of the electronic and optical properties of polyfluorene chains and compare them to those in copolymers containing alternating fluorene and benzothiadiazole or ethylenedioxythiophene units. The introduction of the comonomer can strongly modify the excitonic properties as well as the efficiency of charge-and energy-transfer processes. The choice of the comonomer is thus critical in targeting specific optical properties while maintaining good transport properties.

A joint theoretical and experimental study of the electronic and structural properties of liquid crystalline metal-free phthalocyanines bearing a strong potential for charge and exciton transport has been performed. The synthesis of such compounds has been triggered by quantum chemical calculations showing that: (i) hole transport is favored in metal-free phthalocyanines by their extremely low reorganization energy (0.045 eV) and large electronic splittings; and (ii) the efficiency of energy transfer along the one-dimensional discotic stacks is weakly affected by rotational disorder due to the two-dimensional character of the molecules. We have synthesized two metal-free phthalocyanines with different branched aliphatic chains on the gram scale to allow for a full characterization of their solid-state properties. The two compounds self-organize in liquid crystalline mesophases, as evidenced by optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and molecular dynamics simulations. They exhibit a columnar rectangular mesophase at room temperature and a columnar hexagonal mesophase at elevated temperature.

The microscopic morphology of a series of substituted fluorene-based conjugated polymers and copolymers are analyzed with tapping-mode atomic force microscopy. Different structures are observed depending on the nature of the substituents. Thin deposits of polyfluorenes substituted with linear alkyl groups are made of long fibrils, with lateral dimensions on the order of a few nanometers; polymers with branched alkyl or aromatic substituents form homogeneous, featureless films. To understand how polymer chains pack into these structures, comparisons are made with molecular modeling calculations; the simulation results highlight the dependence between intermolecular π-π interactions and steric hindrance among substituents: linear alkyl substituents allow for a close packing of the conjugated chains into very long, regular π-π stacks, in contrast to the bulkier substituents. A strong correlation is established between the degree of order in the thin deposits and the solid-state photoluminescence spectra; a red shift and the formation of a broad emission band in the green region are observed for deposits showing long-range organization, which is attributed to the formation of aggregates of well-organized, densely packed molecules.

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