The aggregation of conjugated polymers and electronic coupling of chromophores play a central role in the fundamental understanding of light and charge generation processes. Here we report that the predominant coupling in isolated aggregates of conjugated polymers can be switched reversibly between H-type and J-type coupling by partially swelling and drying the aggregates. Aggregation is identified by shifts in photoluminescence energy, changes in vibronic peak ratio, and photoluminescence lifetime. This experiment unravels the internal electronic structure of the aggregate and highlights the importance of the drying process in the final spectroscopic properties. The electronic coupling after drying is tuned between H-type and J-type by changing the side chains of the conjugated polymer, but can also be entirely suppressed. The types of electronic coupling correlate with chain morphology, which is quantified by excitation polarization spectroscopy and the efficiency of interchromophoric energy transfer that is revealed by the degree of single-photon emission.

The particle-like nature of light becomes evident in the photon statistics of fluorescence from single quantum systems as photon antibunching. In multichromophoric systems, exciton diffusion and subsequent annihilation occurs. These processes also yield photon antibunching but cannot be interpreted reliably. Here we develop picosecond time-resolved antibunching to identify and decode such processes. We use this method to measure the true number of chromophores on well-defined multichromophoric DNA-origami structures, and precisely determine the distance-dependent rates of annihilation between excitons. Further, this allows us to measure exciton diffusion in mesoscopic H- and J-type conjugated-polymer aggregates. We distinguish between one-dimensional intra-chain and three-dimensional inter-chain exciton diffusion at different times after excitation and determine the disorder-dependent diffusion lengths. Our method provides a powerful lens through which excitons can be studied at the single-particle level, enabling the rational design of improved excitonic probes such as ultra-bright fluorescent nanoparticles and materials for optoelectronic devices.

Strong dipole–dipole coupling within and between π‐conjugated segments shifts electronic transitions, and modifies vibronic coupling and excited‐state lifetimes. Since J‐type coupling between monomers along the conjugated‐polymer (CP) chain and H‐type coupling of chromophores between chains of a CP compete, a superposition of the spectral modifications arising from each type of coupling emerges, making the two couplings hard to discern in the ensemble. We introduce a single‐molecule H‐type aggregate of fixed spacing and variable length of up to 10 nm. HJ‐type aggregate formation is visualized intuitively in the scatter of single‐molecule spectra.

Excited-state interchromophoric couplings in π-conjugated polymers present a daunting challenge to study as their spectroscopic signatures are difficult to separate from structure-dependent intrachromophoric spectral characteristics. Using custom-designed molecular model systems in combination with single-molecule spectroscopy, a controlled coupling of the excited states between cofacially arranged π-conjugated oligomers is shown to be possible. Multiscale molecular dynamics simulations allow us to generate a representative ensemble of molecular structures of the model molecule embedded in a polymer matrix and examine the connection between structural fluctuations of the molecule with theoretically predicted and measured spectral signatures. The single molecules in the embedding matrix polymer can be assigned to specific conformational features with the help of computer-based "virtual spectroscopy". By combining a quantum chemical approach with an analytical approach, we show that the coupling between the chromophores is well-described by transition dipole coupling above an interchromophoric separation of ∼4.5 Å. Even for aligned chromophores, however, twisting between repeat units of the π-system and bending of the individual π-systems can lead to a decoupling of the chromophores to a degree far beyond what their equilibrium structures would suggest: tiny displacements of the molecular constituents can dramatically impact excited-state interactions. This observation has profound implications for the design of future tunable organic optoelectronic materials.

ABSTRACT:The microscopic orientation and position of photoactive molecules is crucial to the operation of optoelectronic devices such as OLEDs and solar cells. Here, we introduce a shape-persistent macrocyclic molecule as an excellent fluorescent probe to simply measure (i) its orientation by rotating the excitation polarization and recording the strength of modulation in photoluminescence (PL), and (ii) its position in a film by analyzing the overall PL brightness at the molecular level.The unique shape, the absorption and the fluorescence properties of this probe yields information on molecular orientation and position. We control orientation and positioning of the probe in a polymer film by solvent vapor annealing (SVA). During the SVA process the molecules accumulate at the polymer/air interface, where they adopt a flat conformation, much like water