Spotlight on Charge-Transfer Excitons in Crystalline Textured n-Alkyl Anilino Squaraine Thin Films

Prototypical n-alkyl terminated anilino squaraines for photovoltaic applications show characteristic double-hump absorption features peaking in the green and deep-red spectral range. These signatures result from coupling of an intramolecular Frenkel exciton and an intermolecular charge transfer exciton. Crystalline, textured thin films suitable for polarized spectro-microscopy have been obtained for compounds with n-hexyl (nHSQ) and n-octyl (nOSQ) terminal alkyl chains. The here released triclinic crystal structure of nOSQ is similar to the known nHSQ crystal structure. Consequently, crystallites from both compounds show equal pronounced linear dichroism with two distinct polarization directions. The difference in polarization angle between the two absorbance maxima cannot be derived by spatial considerations from the crystal structure alone but requires theoretical modeling. Using an essential state model, the observed polarization behavior was discovered to depend on the relative contributions of the intramolecular Frenkel exciton and the intermolecular charge transfer exciton to the total transition dipole moment. For both nHSQ and nOSQ, the contribution of the charge transfer exciton to the total transition dipole moment was found to be small compared to the intramolecular Frenkel exciton. Therefore, the net transition dipole moment is largely determined by the intramolecular component resulting in a relatively small mutual difference between the polarization angles. Ultimately, the molecular alignment within the micro-textured crystallites can be deduced and, with that, the excited state transitions can be spotted.Comment: 12 pages, 8 figure

The Effect of Chain Bending on the Photophysical Properties of Conjugated Polymers

The impact of chain bending on the photophysical properties of emissive conjugated polymers (CPs) is studied theoretically using Holstein-style Hamiltonians which treat vibronic coupling involving the ubiquitous vinyl/ring stretching mode nonadiabatically. The photophysical impact of chain bending is already evident at the level of an effective Frenkel Hamiltonian, where the positive exciton band curvature in CPs translates to negative excitonic coupling between monomeric units, as in J-aggregates. It is shown that the absorption and photoluminescence (PL) spectral line shapes respond very differently to chain bending. The misalignment of monomeric transition dipole moments with bending <i>selectively</i> attenuates the 0–0 PL peak intensity while leaving the 0–1 intensity practically unchanged, a property which is ultimately due to the uniquely coherent nature of the 0–0 peak. Hence, the 0–0/0–1 PL ratio, as well as the radiative decay rate, decrease with chain bending, effects that are more pronounced at lower temperatures where exciton coherence extends over a larger portion of the chain. Increasing temperature and/or static disorder reduces the exciton coherence number, <i>N</i>_coh, thereby reducing the sensitivity to bending. In marked contrast, the absorption vibronic progression is far less sensitive to morphological changes, even at low temperatures, and is mainly responsive to the exciton bandwidth. The above results also hold when using a more accurate 1D semiconductor Hamiltonian which allows for electron–hole separation along the CP chain. The findings may suggest unique ways of controlling the radiative properties of conjugated polymer chains useful in applications such as organic light emitting diodes (OLEDs) and low-temperature sensors

Exciton mobility control through sub-angstrom packing modifications in molecular crystals

Exciton mobility in pi stacks of organic chromophores is shown to be highly sensitive to the interference between long-range Coulombic coupling and a short-range coupling due to wave function overlap. A destructive interference, which leads to a compromised exciton bandwidth, can be converted to constructive interference (and an enhanced bandwidth) upon sub-Angstrom transverse displacements between neighboring chromophores. The feasibility of the control scheme is demonstrated theoretically on a derivative of terrylene, where the exciton is essentially immobile despite strong Coulombic coupling. A transverse slip of only 0.5 angstrom along either the short or the long molecular axis boosts the exciton velocity to 2 x 10(4) m/s. Changes in the mobility are correlated to changes in the absorption spectrum, allowing the latter to be used as a screen for high mobility aggregates

Modulating Singlet Fission by Scanning through Vibronic Resonances in Pentacene-Based Blends

Vibronic coupling has been proposed to play a decisive role in promoting ultrafast singlet fission (SF), the conversion of a singlet exciton into two triplet excitons. Its inherent complexity is challenging to explore, both from a theoretical and an experimental point of view, due to the variety of potentially relevant vibrational modes. Here, we report a study on blends of the prototypical SF chromophore pentacene in which we engineer the polarizability of the molecular environment to scan the energy of the excited singlet state (S1) continuously over a narrow energy range, covering vibrational sublevels of the triplet-pair state (1(TT)). Using femtosecond transient absorption spectroscopy, we probe the dependence of the SF rate on energetic resonance between vibronic states and, by comparison with simulation, identify vibrational modes near 1150 cm-1 as key in facilitating ultrafast SF in pentacene

Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds

Coupling among chromophores in molecular assemblies is responsible for phenomena such as resonant energy transfer and intermolecular charge transfer. These processes are central to the fields of organic photovoltaics and photocatalysis, where it is necessary to funnel energy or charge to specific regions within the system. As such, a fundamental understanding of these transport processes is essential for developing new materials for photovoltaic and photocatalytic applications. Recently, photocatalytic systems based on photosensitizing perylene monomimide (PMI) chromophore amphiphiles were found to show variation in hydrogen gas (H₂) production as a function of nanostructure crystallinity. The 2D crystalline systems form in aqueous electrolyte solution, which provides a high dielectric environment where the Coulomb potential between charges is mitigated. This results in relatively weakly bound excitons that are ideal for reducing protons. In order to understand how variations in crystalline structure affect H₂ generation, two representative PMI systems are investigated theoretically using a modified Holstein Hamiltonian. The Hamiltonian includes both molecular Frenkel excitations (FE) and charge-transfer excitations (CTE) coupled nonadiabatically to local intramolecular vibrations. Signatures of FE/CTE mixing and the extent of electron/hole separation are identified in the optical absorption spectrum and are found to correlate strongly to the observed H₂ production rates. The absorption spectral signatures are found to sensitively depend on the relative phase between the electron and hole transfer integrals, as well as the diabatic energy difference between the Frenkel and CT exciton bands. Our analysis provides design rules for artificial photosynthetic systems based on organic chromophore arrays