Triplet transfer across a surface-anchored metal-organic-framework heterojunction is demonstrated by the observation of triplet-triplet annihilation photon -upconversion in a sensitizer-emitter heterostructure. Upconversion thresholds under 1 mW cm are achieved. In the broader context, the double-electron-exchange mechanism of triplet transfer indicates that the heterojunction quality is sufficient for electrons to move between layers in this solution-processed crystalline heterostructure.

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Efficient photon harvesting materials require easy-to-deposit materials exhibiting good absorption and excited-state transport properties. We demonstrate an organic thin-film material system, a palladium-porphyrin based surface-anchored metal-organic framework (SURMOF) thin film, that meets these requirements. Systematic investigations using transient absorption spectroscopy confirm that triplets are very mobile within single crystalline domains; a detailed analysis reveals a triplet transfer rate on the order of 10 10 s-1. The crystalline nature of the SURMOFs also allows a thorough theoretical analysis using density functional theory (DFT). The theoretical results reveal that the intermolecular exciton transfer can be described by a Dexter electron exchange mechanism that is considerably enhanced by virtual charge-transfer exciton intermediates. Based on the photophysical results, we predict exciton diffusion lengths on the order of several micrometers in perfectly ordered, single-crystalline SURMOFs. In the presently available samples, strong interactions of excitons with domain boundaries present in these metal-organic thin films limit the diffusion length to the diameter of these two-dimensional grains, which amount to about 100 nm. These results demonstrate potential of SURMOFs for energy harvesting applications.

When chromophores are brought into close proximity, noncovalent interactions (π-π/CH-π) can lead to the formation of excitonically coupled states, which bestow new photophysical properties upon the aggregates. Because the properties of the new states not only depend on the strength of intermolecular interactions, but also on the relative orientation, supramolecular assemblies, where these parameters can be varied in a deliberate fashion, provide novel possibilities for the control of photophysical properties. This work reports that core-substituted naphthalene diimides (cNDIs) can be incorporated into surface-mounted metal- organic structures/frameworks (SURMOFs) to yield optical properties strikingly different from conventional aggregates of such molecules, for example, formed in solution or by crystallization. Organic linkers are used, based on cNDIs, well-known organic chromophores with numerous applications in different optoelectronic devices, to fabricate MOF thin films on transparent substrates. A thorough characterization of the properties of these highly ordered chromophoric assemblies reveals the presence of non-emissive excited states in the crystalline material. Structural modulations provide further insights into the nature of the coupling that gives rise to an excited-state energy level in the periodic structure.

Herein, we present the first investigation of N‐heteroacenes as acceptors in bulk‐heterojunction solar cells. The optical and electronic properties of tetraazapentacene (TIPS‐TAP), triptycenyl‐tetraazapentacene (TIPS‐TAP‐1T), and bistriptycenyl‐tetraazapentacene (TIPS‐TAP‐2T) compounds are characterized by UV‐vis, photothermal deflection, and ultraviolet photoemission spectroscopies. We compare the photovoltaic performance of the N‐heteroacenes and find that cells with TIPS‐TAP‐2T significantly outperform the other derivatives, achieving a power conversion efficiency of 2.5% without extensive optimization or processing additives. We characterize the morphology and order within the active layer by atomic force microscopy and grazing incidence wide‐angle scattering measurements, and find that blends with TIPS‐TAP result in a gross phase separation driven by its strong crystallization. The substitution with triptycenyl units suppresses this crystallization resulting in amorphous films with a finer intermixing and a smooth surface structure. Finally, we investigate the photophysics of charge separation at the donor/acceptor interface and find that it is fundamentally different from the “conventional” polymer‐fullerene systems. In blends with the tetraazapentacene derivatives, exciton dissociation is relatively slow and charge separation is strongly field dependent. We observe improved charge generation and significantly reduced recombination for TIPS‐TAP‐2T as compared to the other derivatives, which in combination with the improved film microstructure is responsible for the enhanced photovoltaic performance.