Interplay Between J- and H-Type Coupling in Aggregates of π-Conjugated Polymers: A Single-Molecule Perspective

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.